Eli Ully and Company 

Lafayette, lndlana Alternative Monitoring Potltlon 

During the autopurge period, rolling average calculations for the pollutants monitored by the Ecochem 

system (HCI, CO, 0,, S02, and NO,) wiU be frozen (similar to when the system Is In calibration mode). 

Once the autopurge period is complete and data is available (approximately 5 minutes), rolling average 

calculations will be unfrozen. The approximate 5-minute time period when the Ecochem is offtlne due the 

autopurge should be considered excused downtime. 

3.3.4.3 PM and HWC MACT Metals Rolling Average Calculations during Ecochem CEMS Dally 

Calibration and Ongoing Quality Assurance Audits 

The stack moisture content measurad by the Ecochem is used to calculate the dry stack nowrate. The 

dry stack ftowrate Is used to determine the rolling average value of the PM emission rate In tenms of 

mgldsan. In addition, the PM CEMS and the Mufti..Metals CEMS use the stack 0, concentration to 

c:oneot measured stack data to 7% oxygen. Since both the stack moisture content and stack 0, 

concentration will be unavailable when the Ecochem Is being calibrated, When performing an ACA, or 

when the probe Is being purged While burning hazardous waste, the rolling average calculations of the 

HWC MACT metals and PM emission rates will be frozen during these periods. This is in addition to 

freezing the rolling average values of the constlluents measured by the Ecochem CEMS (HCI, CO, o,, 

S02, and NO, (See Section 3.3.4.1 ). Specifically, the rolling averages for the Multi-Metals and PM CEMS 

wil be frozen once three consecutive 15-minute average valUes are unavailable in a one hour block 

average period due to calibration or ACA of tho Ecochem, or autopurge of the Ecochem stack probe. In 

addition, Ully w~l consider the time period the rolling averages are frozen as excused downtime. 

3.3.5 Backup to the HCI CEMS 

Lilly wal monitor operating parameter limits defined in Section 1209 of the HWC MACT when the 

incinerator Is In parametric mode. Details of the specific operating limits are provided in the NOC. 

Lilly wUI incorporate delays When transitioning from the CEMS mode of operation to the parametric mode 

of operation. Specifically, once the HCI CEMS is unavailable, the ccntroj system will automatically switch 

to the parametric modo of operation. Rolling averages, related to the Air Pollution Control System 

(APCS), will not start until the system has been under the parametric mode of operation for 10 minutes. 

This 1 <Hninute time period will allow Lilly time to make any adjustments to the APCS to bring the system 

to within the respective operating parameter limits. In addition. up to four hours will be allowed before restarting constituent feed rate rolling average operating parameter limits in order to clear the solid feed 

conveyor system. (Lilly will use Its best efforts to avoid introducing ·new" waste streams from the six ' infeed" conveyors to the final "merge· conveyor that leads to the kiln feed chute during this four hour period. 

However, during initial CEMS mode operation periods there will be practical limitations to this criterion 

beceuse few waste streams wiU have been burned.) Feed rates will be maintained nominaly stable or 

historically tower than when operating in CEMS mode. If the CEMS mode of operation is still not 

52 Rev. 7.0 

VES009400 
Eli U lly and Company 

Lafayette, Indiana Alternative Monitoring Petition 

available after four hours, the transition to parametric mode will be completed an<! only waste with known 

composition will be processed In the incinerator so that consliluent feed rate operating parameter limits 

can be computed. 

3,4 JUSTIFICATION FOR REQUEST FOR ALTERNATIVE MONITORING METHOD 

The HWC MACT final rule (40 CFR 63 Subpart EEE) did not mandaiG the use of CEMS fol parameters 

other than CO, hydrocarbon, oxygen, and particulate matter. (Use of a particulate matter CEMS Is 

defemed until EPA promulgaiGs PM CEMS performance specifications and operational requirements). 

However, as stated in the September 30, 1999 preamble lo the HWC MACT, 64 Fed. Reg. 52925, the 

EPA has a strong preference for the use of CEMS for demonstration of compliance with emission 

standards. The regulatory preference for CEMS aver the use of process operating limits is based on the 

CEMS direct measure of HAPs or surrogate HAPs In the stack gas, a high degree of certainty regarding 

compliance with lhe emission standards, and provision of bauer compliance information to tile public. 

The EPA therefore encourages units like Lilly's to use CEMS In the manner proposed In this petition as 

an alternative to the HWC MACT mandated process parameter C(l()tinuous monitoring of 40 CFR 

63.1209. This Alternative Monitoring Petition ind udes performance specifications and quality assurance 

requirements for each CEMS. 

The use of the PM, multi-metals and HCI CEMS is a significant Investment that l illy has voluntarily 

undertaken In order to receive cenain regulatory incentives. Sucn regulatory incentives allowed to 

facilities using alternative CEMS are outlined in the preamble to the September 30, 1999 final HWC 

MACT rule. The inoentives include relief from the operating parameter limits presaibed In Section 1209 

of the HWC MACT and relief from sampling and analyzing the waste feed streams for asll, merrury, SVM, 

LVM, and HCVCI,. See Table 1 for the operating and emission ll ~s that apply while the alternative 

CEMS are operating. Providing incentives is a key factor for facilities voluntarily operating alternative 

CEMS and encourages the development and Implementation of new and emerging CEMS. 

53 Rev. 7.0 

VES009401 
Ell Lilly and Company 

Lafayette, Indiana Alternative Monitoring Petition 

U ALTERNATIVE MONITORING CANDIDATES UNDER 63.1209(g) 

Lmy has prepared this section ollhe alternative monitoring petition under Section 63.1209(g) ol lhe HWC 

MACT to request relief from certain operating parameter requirements. 

4.1 STACK GAS FLOWMETER DAJL Y CHECK AND AUTOPURGE 

Section 6.2 of the Appendix to the HWC MACT allows facUlties to bum hazardous waste for a ma><lmum 

of 20 minutes while calibrating !he CO and oxygen CEMS. No comparable provision exists in !he HWC 

MACT rule for routine checks of parameter CMS that monitor operating data. However. the General 

Provisions allow such routine checks to occur during normal operation (40CFR part 63.8 (c)). Ully wm 

perform daily routine checks of lhe stack gas flow meter while burning hazardous waste. 

In addition. the probe tip on the flowmeter monitoring !he stack gas flow rate may be purged 

approximately once per day while hazardous waste Is being burned. Purging Involves directing 

compressed air through the probe Into the stack for a short period of time to prevent buildup of SOlids in 

the probe. The purge period will last approximately 5 minutes. Purging the stack probe is neilessary for 

preventive maintenance reasons and is recommended by the manufacluret due to !he types of wastes 

burned in the solid liquid lnclnetation system. 

During the dally checks and auto purge periods, the stack gas ftowrate roiling aVetage catculalions will be 

frozen. Once data is available. rolling average calculations will be unfrozen. Specifically, the first 

available one-minute avet'age value following the autopurge perfod wtll ba added to the most recent 59 

one-minute average values prior to freezing the rolling average calculalions. 

4.2 COMBUSTION GAS FLOW RATE OPERATING PARAMETER LIMIT 

The stack moisture content measured by the Erochem is used to calculate the dry stack nowrate in terms 

of dscf/mln. The dry staCk fiowrate hourty rolling average is compared to the HWC MACT maximum 

combustion gas ftowrale limil The stack moistute content wiU be unavaUable when the Ecochem is being 

calibrated. performing an ACA. or the Ecochem probe is belng purged. Therefore, the romng average 

calculations of the combustion gas flowrato will be frozen during these events. In add~lon . Lilly will 

consider the time period the roUing average Is frozen as excused downtime. 

54 Rev. 7.0 

VES009402 
Ell Lilly and Company 

Lafayette, Indiana Alternative Monitoring Petition 

4.3 CALCULATION Of ROLLING AVERAGES WHEN ALL ONE-MINUTE AVERAGE VALUES 

ARE NOT AVAILABLE 

Lilly requests that the calculation of the one hour rolling average values be allowed to continue provided 

that 95% of the On<H11inute data values, In terms of the apptieable limit, are available Q.e. 57 minutes for 

an hourly roUing average and 684 minutes for a 12-l'lour rolling average). Correspondingly, historical 

storage of the data will be considered complete proVIding that 95% of the values have been captured. 

Purge and catibr.ltlon times are excluded from the 95% calculation. 

This request is based on response to a comment on the April 20, 2004 proposed HWC MACT rule. 

Although, EPA was unable to make the change in the final HWC MACT rule signed September 14, 2005, 

the agency stated that it understands the need for such language and has recommended that sources 

use the provisions of 63.1209{g) to request this alternative monitoring approach. 

55 Rev. 7.0 

VES009403 
Ell Lilly and Company 

Lafayette, Indiana Alternative Monitoring Petition 

5.0 ALTERNATIVE MONITORING PETITION APPROVAL 

Pursuant to Section 63 8(1)(5) of the General PIO\Iisions. lhe Administrator will provide notification of ttle 

approval or intention to disapprove requests made under Section 63.8(1) of the General Provisions within 

30 days of receipt ot the application. and wi1hln ;lQ days after receipt of any supplementary information 

that is submitted. Section 63.1 209(g){1 )(iii)(C) states that the timing for approval of requests under 

§63.1209(g) is that the Administrator will provide notification of the approval or intention to disapprove the 

application wittlln l1Q days of receipt of the application. and within 60 days after receipt of any 

supplementary information that is submitted. 

However, Ully would welcome comments at lhe agency's eartiest convenience sinoe the aHemative 

mooitoring issues Identified in this application affect system design and instrument procurement activities. 

test planning. control system configuration, and completion of MACT compliance plans. 

56 Rev. 7.0 

VES009404 
Ell Lilly and Company 

Lafayette, Indiana AltemaUve Monitoring Petition 

6.0 RELEVANT REFER.ENCES 

1. Performance Specification 11 - Specifications and Test Procedures for Particulate Matter 

Continuous Emission Moni1oring Systems at Stationary Sources, 40 CFR Part 60, Appendix B, 

January 12, 2004. 

2. EPA Draft Guidance Documents on PM CEMS, provided to Eli uny and Company by EPA Office 

of At Quality Planning and Standards March 3, 2005. 

3. Procedure 2· Quality Assurance Requirements lor Particulate Matter Continuous Emission 

Monhoring Systems at Stationary Sources, 40 CFR Part 60. Appendix F, January 12, 2004. 

4. Draft Method 301 Evaluation of candidate Conditional Methods, Cooper Environmental Services, 

LLC .. Volume I, June 10, 2005 

• X-<ay Based Fiher Methods (XFM) 

• MuiU·Metals Instrumental Analyzer Procedure (XACT-IAP) 

• Quantitative Reference Aerosol Generator (QAG) 

5. Draft Standard Operating Procedure for Generating a Quantitative Multi..-netals Reference 

Aerosol with the CES QAG, Cooper Environmental Services, LLC .. Draft Method 301 Evaluation 

of candidate CondiUonal W.ethods Volume II, Appendix C, June 9, 2005 

6. Draft Performance Specification YY: Speciflcalioos and Test Procedures lor X-ray Fluorescence 

Based Mult eta s Continuous Emission Monitoring Systems at Stationary Sources. Cooper 

Environmental Services, UC., Draft Method 301 Evaluation of candidate Conditional Methods, 

Volume II, Appendix F, June 8, 2005 

7. Draft Procedure Z: Quality Assurance Requirements for x .. ay Fluorescence Based Multi-metals 

Continuous Emission Monitoring Systems at Stationary Sources, Cooper Environmental Servlces. 

u c .. Draft Method 301 Evaluation or Candidate Conditional Methods, Volume II, Appendlx F. 

June 9, 2005 

8. Draft Determlnalioo or Metal Emissions from Stationary Sources Using Filters and Solid Sorbents 

with X·ray Fluorescence Analysis, Cooper Environmental Services, LLC., Draft Method 301 

Evaluation of Candidate Conditional Methods. Volume II, Appendix B, June 10, 2005. 

57 Rev. 7.0 

VE$009405 
Ell Lilly and Company 

Lafayette, Indiana Allem allvo Monitor1ng Petition 

9. Standard Operating Procedure for Generating a Quantitative Multi-Metals Reference Aerosol with 

the CES OAG, Cooper Environmental Services. LLC., June, 2005. 

10. Performance Specification 2· Specifications and Test Procedures tor S02 and NOx Continuous 

Emission Monitoring Systems in Stationary Sources, 40 CFR 60 Appendix B. February 2000. 

11. Performance SpecifiCation 4A • SpecifiCations and Test Procedures for C8rtlon Monoxide 

Continuous Emission Monitoring Systems in Stationary Sources, 40 CFR 60 Appendix B, 

February 2000. 

12. Perfonnance Specification 4 B • SpecificaUons and Test Procedures for Carbon Monoxide and 

Oxygen Continuous Emission Monitoring Systems i1 Stationary Sources, 40 CFR 60 Appendix 8 , 

September 30, 1999. 

13. Appendix to Subpart EEE of Part 63- Quality Assurance Procedures lor Continuous Emissions 

Monitors Used for Hazardous Waste Combustors, 40 CFR 63 Subpart EEE, September 30, 1999. 

14. Perfonnance Specification Z: Specifications and Test Procedures For Hydrogen Chloride (HCL) 

Continuous Emission Monitoring Systems At Stationary Sources, Eli Li ly. November 2005. 

15. Procedura DO: Quafity Control and Qualily Assurance Requirements lor Hydrogen Chloride 

(HCL) Continuous Emission Monitoring Sysiems At Stationary Sources, Eli Lilly, November 2005. 

58 Rev. 7.0 

VES009406 
VES009407 .pdf 
Appendix A 

Total Particulate Mass Continuous Emission 

Monitoring System Supporting Documents 

Version 1.0 

November. 2005 

VES009407 
Table of Contents 

I. Perfonnance Specijjcatioo II - Specifications and Test Procedures for Particulate 

Matter Continuous Emission Monitoring Systems at Stationary Sources, 40 CFR 

Part 60, Appendix B, January 12, 2004. 

2. Procedure 2- Quality Assurance Requirements for Particulate Matter Continuous 

Emission Monitoring Systems at Stationary Sources, 40 CFR Part 60, Appendix 

F, January 12,2004. 

3. EPA Draft Guidance Documents on PM CEMS, provided to Eli Lilly and 

Company by EPA Office of Air Quality Planning and Standards March 3, 2005. 

a. Precision and Bias Guidance 

b. Procedure 2 Audits 

c. Procedure 2 Routine Checks 

d. PS II Example Calculations 

e. PS II Spreadsheet Example 

f. Relative Calibration Audit Dala Evaluation 

g. Stratification Procedure 

VES009408 
VES009409 .pdf 
Appendix B 

X-ray Fluorescence Based Multi-Metals Continuous 

Emission Monitoring System Supporting Documents 

Version 1.0 

Non mber, 2005 

VES009409 
Table of Contents 

1. Draft Method 30 I Evaluation of Candidate Conditional Methods, Cooper 

Environmental Services. LLC., Volume I, June 10,2005. 

a. X-ray Based filter Methods (XFM) 

b. Multi-Metals Instrumental Analyzer Procedure (XACT-IAP) 

c. Quantitative Reference Aerosol Generator (QAG) 

2. Draft Performance Specification YY: Specifications and Test Procedures for X-ray 

Fluorescence Based Multi-metals Continuous Emission Monitoo·ing Systems at 

Stationary Sources, Cooper Environmental Services, LLC., Draft Method 30 I 

Evaluation of Candidate Conditional Methods, Volume U. Appendix F, June 8, 2005 

3. Draft Procedure Z: Quality As.~urnnce RequirementS for X-ray Fluorescence Based 

Multi-metals Continuous Emission Monitoring Systems at Stationary Sources, 

Cooper Envirorun~ntal Services, LLC .. Draft Method 301 Evaluation of Candidate 

Conditional Methods, Volume U, Appendix F, June 9, 2005 

4. Draft Dctennination of Melal Emissions from Stationary Sources Using Filters and 

Solid Sorbents with X-ray Fluorescence Analysis, Cooper Environmental Services, 

LLC., Draft Method 301 Evaluation of Candidate Conditional Methods, Volume II, 

Appendix B, June I 0, 2005. 

5. Standard Operating Procedure for Generating a Quantitative Multi-Metals Reference 

Aerosol with the QAG, Cooper Environmental Services, LLC,. June 2005 

VES009410 
VES009411 .pdf 
Candidate Conditional Method ZZ: 

Determination of Metal Concentration in CES' Xact 

CEMS Stilling Chamber Using Filters and Solid 

Sorbents with X-Ray Fluorescence Analysis 

Prepared by: 

Cooper Environm ental Services, LLC 

IOIRO SW Nimbus Blvd Suite J6 

Ponland, Oregon 97223 

Re'\<ision 1.0 

June, 2005 

VES00941l 
Candidate 

Condition 

alMethod 

ZZ: 

Determination of Metal Concentration in CES' Xact 

CEMS Stilling Chamber Using Filters and Solid 

Sorbents with X-Ray Fluorescence Analysis 

Draft 

June 23, 2005 

Prepared for 

U.S. Environmental Protection Agency 

Research Triangle Park, NC 

Prq1ared by: 

J.A. Cooper, B.E . .Johnsen, K. Petterson, 

C. A. Yanca, M. Nakanishi, 0 . Barth, S. Fry 

VES009412 
Cooper En•ironmeotal Servi«S, LLC 

10180 SW Nimbus Blvd Suite J6 

Portland, Oregon 97223 

VES009413 
Candidate Conditional Method ZZ: 

Determination of Metal Using Filters and Solid 

Sorbents with X-Ray Fluorescence Analysis 

Prepared =---~=-- Date: _ _ _ 

Douglas C. Barth, Environmental Scie,ntist 

Prepared by: Date: __ _ 

Cay A. Yanca, Environmental Scientist 

Prepared by: Date: __ _ 

Krag Petterson, Environmental Scientist 

Reviewed by: Date: __ _ 

Bruce E. Johnsen, QA Manager 

Approved by: Date: _ _ _ 

John A. Cooper, Director 

VES009414 
Executive Summary 

Eli Lilly and Company (Lilly) operates a waste incineration system located at the Tippecanoe 

Laboratories in Lafayette, Indiana. This incinerator system includes an Xact multi-metals 

continuous emissions morut()ring system (Xact-CEMS, manufactured by Cooper 

Environmental Services.LLC) for demonstrating attainment with the Hazardous Waste 

Combustor MACT for semi-volatile metals, low-volatile metals, and mercury emissions. 

Lilly must conduct an initial performance evaluation test as well as quarterly and annual 

audits to assure the accuracy of the reported results from the CEMS. LiUy has proposed the 

use of a NIST -traceable reference aerosol generator for relative accuracy and lineariry 

determinations. lu addition, Lilly is also proposing the use of a new sampling and analysis 

reference method for metals to assure the accumcy of the spiked reference aerosol. 

This appendix. describes this new sampling and analysis method used in Method 301 tests 

described in the body of this report and proposed for the above noied irutial performance 

evaluation test and annual audits of LiUy's Xact-CEMS. This new method is an X-ray Based 

Filter Method (XI'M) tllat drdws a representative sample of incinerator emissions from the 

Xact-CEMS stilling chamber through a series of reactive and non-reactive !ilters. The filter 

deposits arc non-destructively analyzed by X-Ray Fluorescence (XRF) to determine metal 

concenlrlltions in the filter deposits. Metal concentrations in th.e emissions are calculated by 

dividing the volume of sampled flue gas into the metal mass measured by XRF. 

This method is applicable to the measurement of chromium (Cr), arsenic (As), cadrruum 

(Cd), mercury (Hg), and lead (Pb)) in emissions from Lilly's hazardous waste incinerator. 

Ald10ugb tile XFM is optimized for these elements, it is applicable to other elements 

including: ''anadium (V), manganese (Mn), iron (Fe), nickel (Ni), copper (Cu), zinc (Zn), 

silver (Ag), antimony (Sb), barium (Ba), thallium (TI), tin (Sn), bismuth (Bi), cobalt (Co) and 

selenium (Se). The XFM can quantify flue gas concentrations ranging from less than 0.2 to 

over 2000 ~g/dscm. 

Page i ofi 

VES009415 
Table of Contents 

Executive Summary ................................................................................................................... i 

i~t of Symbols ........................................................................................................................ iv 

List ofFigures ............................................................................................................................ v 

1.0 Method Summary .......................................................................................................... I 

1.1 Principle ................................................................................................................ I 

1.2 Applicability ......................................................................................................... I 

1.3 Cautions ................................................................................................................ I 

2.0 Definitions and Abbreviations ...................................................................................... 2 

3.0 Safety ............................................................................................................................ 2 

4 .0 Apparntus ...................................................................................................................... 2 

4.1 Overview ............................................................................................................... 2 

4.2 Extraction assembly .............................................................................................. 3 

4.3 Extrnction flow control module ............................................................................ 3 

4.4 Dilution flow control module ................................................................................ 3 

4.5 Sample filter holder assembly ............................................................................... 3 

4.6 Sample flow control module ................................................................................. 3 

5.0 Reagents and Standards ................................................................................................ 4 

5.1 Filter caSllette ........................................................................................................ 4 

5.2 Desiccant ............................................................................................................... 5 

5.3 XRF standards ....................................................................................................... 5 

6.0 Pre-sample Preparation ................................................................................................. 5 

6.1 Test preparation .................................................................................................... 5 

6.2 Pre-test 13boratory preparation .............................................................................. 5 

6.3 Sample train preparation ....................................................................................... 5 

7.0 Sample Collection ......................................................................................................... 6 

7.1 Filter holder leak check ......................................................................................... 6 

7.2 Setting total flow needle valve .............................................................................. 6 

7.3 Filter temperature range ........................................................................................ 6 

7.4 Evaluation of sample meter accuracy ................................................................... 6 

7.5 Filter cassette installation ...................................................................................... 7 

7.6 Sampling ............................................................................................................... 7 

Page ii ofv 

VES00941 6 
7. 7 Sample recovery .................................................................................................... 7 

7.8 Post-test Checks .................................................................................................... 7 

8.0 Sample Recovery, Handling a.nd Preservation .............................................................. 7 

9.0 Elemental Analysis ....................................................................................................... g 

9.1 Analysis ................................................................................................................. 8 

9.2 Calibration ............................................................................................................. 8 

10.0 Calculations ................................................................................................................... 8 

10. 1 Flow Correction Factor ......................................................................................... 8 

10.2 XFM Measured Aerosol Concentration ................................................................ 9 

11.0 Quality Control ............................................................................................................. 9 

11.1 Sampling ............................................................................................................... 9 

I 1.2 Analysis ................................................................................................................. 9 

12.0 Method Performance ..................................................................................................... 9 

12. 1 Range .................................................................................................................. 10 

12.2 Detection Limits .................................................................................................. I 0 

13.0 Pollution Prevention. ................................................................................................... 10 

14.0 Waste Management ..................................................................................................... 10 

15.0 Tables and Figures ...................................................................................................... I 0 

16.0 References ................................................................................................................... 17 

Page iii ofv 

VES009417 
List of Symbols 

c,~mt • Concentration of the ;•h analyte in the emission measured by the XFM 

M,l'11'£ • XRF-detennined mnss of the;"' analyte on the PTFE filter 

M,fll!o-?. XRF-dotennined mass of the ;•h aualyte on the reactive filter (RE0-7) 

v: TJJ a Total volume (emission plus dilution) sampled by the XFM 

Vfn' Q Volume of dilution air drawn through filters of the XFM 

Page iv ofv 

VES009418 
List of Figures 

Figure I Flow diagram of the sampling train used in Phase I and ll XFM validation tests . .. 12 

Figure 2: Sample train components used in Phase I and U XFM validation tests .................. 13 

Figure 3: Exploded view of the extraction assembly .............................................................. 14 

Figure 4: Schema tie diagram of the extraction flow control module . .................................... 14 

Figure 5: Schematic diagram of the dilution flow control module ......................................... 15 

Figure 6: Exploded and assembled view of the sample fi lter holder ...................................... 15 

Figure 7: Schematic diagram oflbe sampling flow control module ....................................... 16 

1112'9Jl(ltQ! 3:45PM Page v ofv 

VES009419 
1.0 Method Summary 

1 .I Principle 

A representative sample of flue gas is drnwn from an Xact CEMS1 stilling chamber through a 

cassette containing PTFE and reactive filters. The element:; in particulate matter (PM} are 

deposited on the PTFE filter while the vapor phase elements are trapped on the reactive filter. 

The elemental mass in each filter deposit is determined by X-Ray FluoreS(;ence (XRF} using 

EPA 10 Compendium Method 3.31

. Metal concentrations in stilling chamber flue gas are 

calcu Ia ted by dividing the volume of the flue gas sampled into the elemental mass measured 

by XRF. 

1.2 Applicability 

This method is applicable to the measurement of metal aerosol concentrlltions in the XactCEMS stilling chamber. 

1 .2. 1 Analytes 

This method is applicable to Antimony (Sb), Arsenic (As), Cadmium (Cd), Chromium (Cr), 

Cobalt (Co), Lead (Pb), Ma.nga.nese (Mn), Mercury (Hg), Nickel (Ni), and Selenium (Se) and 

is generally appropriate for elements with atomic number f1om about 13 (AI) through 92 (U) 

as noted in 10 Compendium Method 3.3. This sampling melhod is also applicable to 

Beryllium (Be), if measured with 10 Compendium Method 3.4l after non-destructive XRF 

analysis. 

1 .2.2 lmerferences 

There are no known flue gas components in their typical concentrlltions !hat interfere wilh 

sample collection. Elemental interferences are addressed in 10 Compendium Method 3.32

• 

1.2.3 Concentration Range 

The applicable concentration range of this method is from less tban 0.2 l!g/dS(;m (Table I) to 

over 2000 l!gldscm. 

1.3 Cautions 

This melhod does not include all of !he specifications essential to its performance. Some 

material is incorporated by reference. Therefore, to obtain reliable results, persons using this 

method should have a thorough knowledge of at least EPA Methods 1

4 and 25 and EPA 10 

Compendium Method 3.32

• 

I 1/29/2005 XFM f(lf Xa.et..CEMS SOP VI Page I of 17 

VES009420 
2.0 Defmitions and Abbre,•iations 

Accuracy: The agreement between an experimentally determined value and the true value. 

Ae,rosol: A suspension of solids aod/or liquids in a gas. 

AoaJyte: A species (clement, metal, etc.) of interest in an analytical method. 

Detection Limit: l11c lowest concentrntion of an element that can reliably be distinguished 

from a zero concentration. 

Interferant: A substance other thao the analyte that causes an undesired positive or negative 

output. 

NJST: U. S. Department of Commerce, National institute of Standards and Technology, 

Gaithersburg, MD 20899 

Uncertainty: An indication of the degree of reliability of a value usually expressed 

statistically (probability) as a multiple of the standard deviation of a set of measurements. 

Unless otherwise stated, the uncertainty in a mean value of a series of measurements will be 

the ~"tandard deviation. In the case of values based on calculations, the unconuinty in the 

value is equal to the propagated uncertainty based on the uncertainties in the parameters used 

in the calculations. 

3.0 Safety 

This method involves the measurement of hazardous materials and the operation of 

equipment with the potential to cause bodily harm. This test method does not address 

appropriate safety and health practices associated witb its use. It is tl1e responsibilily oftbc 

user of this test method to establish appropriate safety and health plans prior to perfonning 

this method. 

4.0 Apparatus 

l11e sample collection apparntus used for this method is described in the following 

subsection. The equipment required for the XRF analysis of the filters is specified in 10 

Compendium Method 3.32

. 

The sample collection equipment consists of the following five major components (Figure I 

and figure 2): 

• Extraction assembly 

• Extraction flow control module 

• Dilution flow control module 

1112912005 XFM rar act~EMS SCW VI Page 2 of 17 

VES009421 
• Sample filter holder assembly 

• Sample flow control module 

4.2 Extraclio11 assembly 

The extraction assembly (Figure 3) is usec.l to draw flue gas from the Xact ~'tilling chamber 

d1rough the extraction plate via the extraction flow control module (Subsection4.3). A sul>-

sample of this flow is drawn from the elttraction assembly through the probe plate by the 

sample fl ow control module (Subsection 4.6). A dilution plate is directly downstream of the 

probe plate and the stack gas sample is diluted and mixed with CDA prior to passing through 

the filter holder (Subsection 4.5). 

4.3 Extraction flow control module 

This module (Figure 4) uses an eductor to draw flue gas through the extraction assembly. 

The flow rate is controlled by n standard industrial pressure regulator with gauge and 

powered by compressed CDA. The flue gas is then filtered, dried, and denuded of corrosive 

materi11l before it is elthausted back into the stilling chamber. 

4.4 Dilution flow comrol module 

The dilution flow control module (Figure 5) dries, cleans, controls, measures and totalizes the 

flow of dilution gas. Clean, dry, compressed air is further dried in this module before it is 

used to dilute the sample flue gas. TI1e dilution gas flow and pressure are controlled with a 

regulator, pressure gauge and a needle valve. The flow rate is measured by a mass flow 

meter (D-MFM). A dilution flow integrator (DFI) totalizes the output from the 0 -MFM and 

reports the total volume of dilution air that has been udded to the gas stream. 

4. 5 Sample filte r holder assembly 

TI1e sample filter holder assembly (Figure 6) is used to trap particulate and vapor phase 

metals in the emission sample. Two filters are contained within a 37 mm polypropylene 

filter cassette inside the ftlter holder. The first ftlter is non-reactive PTFE filter and is used to 

tmp patticulate phase metals. The second filter is a reactive filter that collects vapor phase 

metals6

. Downstream of the filters, a thermocouple provides temperature information to 

ensure. that the filters remain within their optimal temperature range of 100• to 180"F. This 

assembly includes a quick disconnect for usc with leak cbccks. 

4.6 Samplejluw c:untrul module 

This module (Figure 7) controls the flow rate of diluted flue gas tl1r0ugh the filters and 

measures the total sample flow. After passing tl~rougb t11e filters, the gas is dried and 

corrosive species removed prior to detennining the dry gas flow rate with a mass flow meter. 

4.6.1 Desic:c:anl Dtyer 

Downstream of the filler holder, a desiccant dryer is used to remove moisture prior to flow 

measuremcnL The XFM reports concentrations as mass per dry standard volume. 

li1291200S, XFM ror Xx1..CEMS SOP VI Page3ofl7 

VES009422 
4.6.2 Corrosive Trap 

Following the desiccant dryer, the diluted flue gas is drawn through a corrosive trap designed 

to remove corrosive flue gns species. 

4.6.3 Total Flow MFM 

The total mass flow meter (T-MFM) measures the total flow (I -2 dslpm) passing through the 

filters. This flow meter produces a 4-20 mA signal which is read and totalized by the total 

flow integrator (TFI). The total sample volume is calculated by subtracting the dilution 

volume from tbe total volume. 

4.6.4 Vac tnnn Ga.uge 

A vacuum gauge capable of reporting a vacuum between 0 and 29 in. Hg is used to ensure 

that a vacuum can be maintained in the XFM during leak checks. Monitoring of this gauge 

during sample collection provides continuing quality assurance of vacuum and filter 

integrity. 

4.6.5 Needle Valve 

A needle valve is used for fine control of the total flow rate during sampling. GeneraUy, little 

adjustment of the needle valve is necessary after the initial adjustment to achieve the desired 

flow. 

4.6.6 1\vo-way Valve 

A manual two-way valve located just upstream of the vacuum pump is used to perform presample leak checks. This valve can also be used as a course flow adjustment to regulate lhe 

tOtal flow passing through the filtec. 

4.6.7 Vacuum Pump 

A diaphragm vacuum pump is used to pull the emission and dilution gas sample through the 

filters. Tbe filtered, cleaned and dried gas sample that passes through the pump is then 

returned to the stack. 

5.0 Materials, Reagents and Standards 

S. I Filter cassette 

One 37 nun diameter PTFE (Teflo7 or equivalent) and one 37 nun diameter RE0-78 filter for 

trapping particulate and vapor phase metals are required by this method for each run. The 

two filters should be pre-loaded into a labeled 37 mm diameter filter cassette in a clean, dry 

environment prior to the test run. Filter cassettes should be stored in a labeled Petri dish 

before and after sampling. 

Page4 of 17 

VES009423 
5.2 Desiccant 

The XFM sample dryer requires an indicating desiccant (Agilent Silica Gel Grade 409 or 

equivalent). A single dryer canridge may be used for multiple runs as long as the desiccant 

remains below the removal capacity specified by the manufacturer. 

5.3 XRF standards 

XRF thin-film standards for metals of interest should be used to calibrate the XRF prior to 

operation according to IO Method 3.~ Standards should have a known mass per area 

()Jg/cm') to within five percent. 

6.0 Pre-sample Preparation 

6. I Test preparation 

The complexity of this method is such tltat, in order to obtain reliable results, both testers and 

analysts must be trained and experienced with the test procedures, including source 

sampling; sample handling; safety equipment and procedures; analytical calculations; 

reporting; and the specific procedural descriptions throughout tllis method. 

6.2 Pre-test laboratory preparation 

Check filters visually against light for irregularities, !laws, or pinhole leaks. Prior to 

shipping, load one upStream PTFE filter and one downstream RE0-7 fllter for each run into a 

labeled filter cassette and place into a labeled Petri dish for transport. Provide one loaded 

filter casset1e for a QA field blank. 

Before each series of tests, the now rates for both the total flow and the dilution flow 

integrators should be checked against a certified NIST-traceable meter. The flow reading on 

the integrator should be within five percent of the reading on the certi'fied NIST traceable 

meter. 

6.3 Sample rranz preparation 

6.3.1 Sample flow rates and samp/1! time 

Sample and dilution flow rates may range from 0.5 to 1.0 slpm, but should not vary by more 

than ten percent during a test run. Sample time should be between 10 and 50 minutes. 

6.3.2 Extraction assembly and dilutionflow mod11le leak checks and sampling rate 

The extraction and dilution assembly muSt be leak checked prior to mounting on the XactCEMS sampling port. To perform this leak check, cap the port adaptor with a rubber Stopper 

and insert the extraction assembly plug (Figure 3). Connect the dilution line for compressed 

air to the dilution plate port and cap the 3f8"extrnction plate port. Pressurize the a.~semb y to 

5 psi and close the dilution flow shut-off valve. The gauge reading should be stable (±5%) 

for 30 seconds. Following a successful leak check, remove the stopper and 3/8" cap nut. The 

11'29.12005 XrM for X.11e....CEMS sor VI Page 5 of 17 

YES009424 
extraction assembly and dilution line can now be mounted on the Xact-CEMS stilling 

chamber sampling port 

The now from the Xact-CEMS stilling chamber through tbc extraction assembly should be 

main~aine<.l in the range of 15-30 slpm. The XFM extraction assembly temperature should be 

above 220°F. 

7.0 Sample Collection 

7.1 Filter holder leak check 

A filter bolder leak check must be perfooned ufter the filter cassette has been loaded in the 

filter holder. To pcrfomttbis check, seal the fi lter holder assembly with the filter holder cap 

nut (Figure 6), tum on the pump and allow the vacuum to reach 15 in Hg. Close the sample 

Oow shut-off valve (Figure 4), tum off the pump, and record the initial pressure and the 

pressure after 30 seconds. To pass this check, the change in pressure must be less than five 

percent of the initial pressure. Disengage the sampling train quick disconnect to release the 

vacuum (figure 6). 

7.2 Setti11g total flow needle 1'(1/ve 

The total flow rate (sample and dilution) that passes Urrough the filter is controlled by a 

needle valve (Figure 7). To determine the needle valve's initial set point, plaoe a loaded 

blank filter casseuc into the filter holder and leak check as stated above. Install the filter 

holder onto the extraction assembly, wlticb is at openting conditions. Open the sample shutoff va lve fully and turn on the sample pump. Set the needle valve so that the T-MFM reads 

the desired sampling rate. Then close the shut-off valve and turn off the pump. For each 

sample run, the shut-off valve wiU be used to start the sampling now while the needle valve 

should be used to make minor flow adjustments as needed after the sampling has started. 

7. 3 Filter temperature range 

Since filter holder temperature can increase at the start of tbe run, it is recommended that the 

filter temperature be maintained at about 140°F before sampling begins and should not 

exceed ISO•F at any time during sampling. 

7.4 EvaluatiOil of sample meter accuracy 

Prior to the first run, the accuracy of the T-MFM should be checked using a NIST-traceable 

flow meter nod stack gas. Mount the filter bolder containing a filter cassette, attach the N'ISTtraceable flow meter to the sample flow outlet, tum on the sample pump, open the ball valve 

and allow stack gas to pass through the filter, T -MFM and NIST-traceable meter. Compare 

the T-MFM value to the NlST flow meter. The values should be within tive percent. If they 

differ by more than five percent, a correction should be made using the fonnula in Section 

I 0.1. Disconnect the NIST flowmeter and place a new filter cassette in tbe filter holder 

before starting the fmt sample run. 

111291200SXFM for Xact<EMS SOl• VI Page6 of 17 

VES009425 
7.5 Filter casselte installatiOII 

For each run, fill out the XFM Field Darn Sheet (Tnble 2), identifying the date, run, opemtor, 

XFM module !.0. no., and filter J.D. numbers, and date, time, and other data for the test run. 

Insert filter cassette into the filter holder and conduct a filter holder leak check. 

7.6 Sampling 

Prior to sampling, zero the total flow integrator. At a time concurrent with the srnrt of an 

Xact sample run, start the XFM sample pump. open the ball valve, and record the initial 

dilution volume and stan time. Sample for 10 to 50 minutes, recording tempcrarures, 

pressures, and volumes every five minutes. Use the dilution and total flow needle valves to 

ensure that the flow rates are constant and monitor the filter temperature to ensure that it 

remains below 180"F. When sampling is complete, close the shut-off valve, tum off the 

vacuum pump and immediately record the dilution volume, total volume and sample run end 

lime on the work.sbeet. 

Note: It is recommended that a post-rest sample flow leak check not be conducted since the 

test may compromise the sample collected on the filter. 

7. 7 Sample recovery 

After removing the filter holder from the extraction ossembly, disa.~semb e the filter holder 

and remove the filter cassette. Return the filter cassette with filters to the original Petri dish, 

and seal tbe dish with tape. Do not separate the PTFE and reactive filters from the filter 

cassette. Document any abnormalities on tbe filter and ship to tbe appropriate laboratory for 

analysis. 

7.8 Post-tesr Checks 

The following checks need to be made after the last test run is complete and before packing 

the equipment for return shipment. 

7.8.1 Flow Agreement Check 

Calibration of the dilution and total mass flow meters should be checked following the same 

procedure as in subsection 7.3. 

7.8.2 E.waction assembly a11d dilurionjl<nv module assembly leak checks 

The extraction a.~embly and dilution flow module leak check should be perfonned according 

to tbe same procedures found in subsection 6.3. 

8.0 Sample Recovery, Handling and Preservatioll 

Open the filter cassettes in a clean work area and note the condition of the filters. Carefully 

remove the filters from the filter cassettes aod place each filter sampling side up in a 

separately labeled Petri slide. Filters should be stored in archives at temperatures less than 

11~!~\C b Xacc.CEMSSOPVI Page 7 of 17 

YES009426 
s•c. The filters remain in archives until they are scheduled for analysis. Following XRF 

analysis tbe fillers may be returned to storage and analyzed again at a later date or they may 

be submitted for analysis for beryllium (Be) according to the procedures outlined in 

Compendium Method 10 3.4. 

9.0 Elemental Analysis 

9.1 Analysis 

TI•e analytical procedures are similar to those in Compendium Method I0-3.32"Standard 

Operating Procedure for the X-Ray Fluorescence Analysis ofPM2.s Deposits on Teflon 

Filters". These methods address the application of energy dispersive X-ray fluorescence 

spectrometry (EDXRF) to the detennination of elemental coinposition of particulate matter 

deposits on filters. 

9.2 Calibration 

The X-ray fluorescence analyzer is calibrated using thin film standards of a k.nown 

concentration (usually in 11g/crn'). Potential manuf.1crurers of thin fihn standards are listed in 

Compendium Method 10-3.3 For each element, a calibration sensitivity factor is obtained by 

dividing the x-ray intensity (counts/sec./rnA) by the concentration of the standard (11glcm'). 

Generally these standards are larger than the area of the exciting X-ray beam while the XFM 

deposition spot is smaller than the beam. For this reason, a thin film to spot ratio must be 

established during calibration. This thin film to spot ratio is determined empirically by using 

a single standard of a known concentration with the same area as the XFM deposition spol 

This ratio is determined for each analysis condition and is applied to each element in that 

analysis condition. 

10.0 Calculations 

JO.J Flow Correction Factor 

Before each series of tests, the now rates for both the total integration and the dilution 

integrator should be checked against a certified NIST-traceable meter. The now reading on 

the integrator ( FFJ) should be within five percent of the reading on the certified NIST 

traceable meter ( F,.,., ) and recorded in the field notes. lf they are not within five percent, the 

noted difference must be used to calculate a correction factor ( CF,) as defined below: 

Equation 1 

llll9!200..S XFM for X11ct-C£MS SOP VI Page 8 of 17 

VES009427 
10.2 XFM Measured Aerosol Concentration 

The XFM-detennined concentration of tb.e five MACT metals in the sampled flue gas is 

based on a measurement of the metal mass deposited on the XFM filters and the sample 

volume that passed through the filters. The XRF analysis results yield the rnetul masses in 

11& of each reported metal per filter. The total sample volume is determined by subtracting 

the dilution volume from the total volume. These parameters are used in Equation 2 to 

calculate the concentration of each analyte as shown below: 

Ml'f'FP. M'E()...' c ,..XFJI = I + I 

I y.rF>I _ y XFU , d Equaoon 2 

Where: 

Ct"'" ~ Concentration of the i'h analyte in the emission measured by the 

XFM (11g/dscrn) 

M ;m = XRF~erennined mass of the ilh anal)'le on the PTFE filter (11&) 

M,R£o-' = XRF«tennined mass of the i

111 analyte on the reactive filter 

(REO-7; 11&) 

v;...., = Total volume (emission plus dilution) sampled by the XFM (dscm) 

V/"" = Volume of dilution air drawn through filters of the XFM (dscm) 

11.0 Quality Control 

1/.1 Sampling 

The sampling quality control requirement• include perfonning all necessary leak checks and 

checking the flow readings against a NlST traceable standard. The following is a list of all 

necessary sampling quality control procedures. 

I. EXtraction assembly leak check (See subsection 6.3) 

2. Dilution assembly leak check (See subection 6.3) 

3. Sample filter holder assembly leak check (See sub.~ection 7.1) 

4. Flow calibration check (See subsection i .3) 

11.2 Analy.tis 

Quality conrrol and assumnce procedures are perfonned in accordance with Compendium 

10-3.3. 

12.0 Method Performance 

11/29!lOOS XfM (Or Xaet...C~;;MS SOP VI Page 9 of 17 

VES009428 
I 2.1 Rtmge 

The applicable concentration rnnge is from less ihnn 0.2 1•g/dscm to over 2000 jlg/dscm. 

I 2.2 DeJection Limils 

The interference free detection limits ut the 95% confidence levelr ...... ! o .. k .. ork •• • •dl•"'· are 

given in Tobie I a$Suming a sampling rate of0.7 slpm and a sampling time of30 minutes. 

Actual meihod detection limits are based on actual source sampling and analytical results. If 

required, the method in- 1ack detection limits can be improved over those shown in Table I 

by either increasing the stack gas volume sampled, the sample time, or XRf analytical time. 

Increasing ihe volume sampled by a factor of two results in a corresponding two fold 

increase in the detection limits. XRF detection limits improve with the square root of the 

analysis time. 

13.0 Pollution Prevention 

The exhaust from the sample flow module is vented to the otmosphere after passing through 

lhe sampling filters, dryer and corrosive gas denuder. There are no reagem solutions 

generated in this method. 

14.0 Waste Management 

Sample lilters are archived for one year and !ben disposed as non-hazardous waste. 

15.0 Tables and Figures 

Table }· XFM Detection LimitsEnM llool;m>tk not defined. 

Element Symbol Analytical In-stack 

. {l!l!ISJ)Otl lualdscm) . 

Antimony Sb 23.0 2.20 

Arsenic As 1.3 0.12 

Cadmium Cd 13.0 12 

Chromium Cr 1.3 0.12 

Cobalt Co 1.3 0.12 

Lead Pb 1.7 0.16 

Manganese Mn 1.3 0.12 

Mercury Hg 2.1 0.20 

Nickel Ni 0.8 0.08 

Selenium Se 1.3 0.12 

Silver Ag 8.4 0.80 

Page 10 of 17 

VES009429 
Date 

Run No. 

Opemtor(s): 

XFM Module No . 

PTFE Filter No. 

RE0-7 Fitter No. 

Pre-test Filter EvaJ. 

Leak Check 

Posl-test Filter Ev. 

Ext 

Time Temp. 

"F 

NOTES: 

Table 2. XFM Field Data Sheet 

XFM FIELD DATA SHEET 

Start Time 

Stop Time 

A) !nit. Tot. Vol. (Oil. Air) 

B) Final Tot. Vol. (Oil. Air) 

C) 0 11. Air for Test (B-A) 

D) Initial Total Vol. 

E) Final TOOl! Vol. 

F)Total Test Vol. (E·D) 

G) Net Sample Vet (F-C) 

Filter Samp. Oil. Flow 

Dll. Ext 

Flow Flow Temp. Flow Flow Vac. Pres. Vac. 

•F liters liters in. Hg in. Hg in. Hg 

llfl9.'200.S Xllol for Xx•<EMS soP VI Page II of 17 

Ext. Drier Flow 

Pres. Pres. 

ln. Hg ln. Hg 

VES009430 
Extraction 

Assembly 

Filter Holder 

Assembly 

. """ [J~; i 

xtracti~ !!~~ con1roJ1 

~ 

l~~ 

.. -----

Dilution Flow Control 

Module 

""" Sample Flow Control 

+ Module 

~= :J J Fiaure l Flow diagram of the sampliug traiu used In Phase I aud II XFM valldation 

tests. 

ttl29/lOCH XFM r.,. x..o.ca.ts sor v1 !'age 12 of 17 

VES00943l 
Olk.IOOn F1ow Co tr~ Mod\le 

,-- ---- -- --- ---- ---- -------·~~

Extmcdon FlOw COn1rQI Moc:f\MJ -- -- -- ------- M·-- ----- ~--- ---~ 

' ' ' ' ' ' 

--------------------- oe:s;;~ . ' ~».-... • ~· ' ' ' ' .......... O"JAt """' ' : 

' -- : '-----------·-------------------------' 

Figure 2: Sample train components used in Pbas<> I and ll XFi\'1 validadon tests. 

Page 13 ofl7 

VES009432 
-

--

£ •1Nrl•lfl 

Aurni~ 

... 

......... 

--.... 

-

••• 

Oiknloo ....... 

Figure 3: Exploded view of the extractlou assembly. 

0.. ~ 

Figure 4: Schematic diagram of the extraction 

-

now control module. 

Page i4ofi 7 

VES009433 
, .--:;;n__ - ... ....... 

r. r.-:: ... ..... ,., FigureS: Schematic diagram of tbe dilution flow control module. 

PWI:! Wa!l~ 0 T~ CamtiC Rlncl 

I Rl ;:Cf I I ... .,.;,: ... ,.. 

Figure 6: Ex:ploded and assembled view of the sample filter bolder. 

11'29r.OOS XFM I(" X ... -CEMS soP VI Page 15 of l7 

VES009434 
·-- ~r======:::;tr=! ~ 

-

__ ..r., 

- -- ll!lfllfltr,.. Vo.-wm ~C\'lle llall y111111.,. 

Ncu Ollop: Vdw \'.rw fiM¥ 

Figure 7: Schematic diagram or the sampling Dow control module. 

Page 16 of 17 

YES009435 
16.0 References 

Xact-CEMS. X-ray Bused Continuous Emissions Monitoring System for Multi-Metals. 

Manufactured by Cooper Environmental Services, LLC. Portland, Oil 

www.cooperenviron.meotal.com. 

2 EPA Compendium of Methods for the Detennination of Inorganic Compounds in 

Ambient Air. June, 1999. Compendium Method 10-3.3 Detem1ination of Metals in 

Ambient Particulate Motter Using X-Ray Fluorescence (XRF) Spectroscopy. EPN625/R96/010a. 

3 EPA Compendium of Methods for the Determination of Inorganic Compounds in 

Ambient Air. June, 1999. Compendium Method I0-3.4 Determination of Metals in 

Ambient Particulate Matter Using Inductively Coupled Plasma (ICP) Spectroscopy. 

EPN625/R-96/010a. 

4 EPA Method I. Sample and Velocity Traverses for Stationary Sources. 

5 EPA Method 2. Determination of Stack Velocity and Volumetric Flow Rnte (TypeS Pitot 

Tube). 

6 NIST. National Institute of Standards and Techoclogy. Gaithersburg, Md. 

www.NJST.gov. 

7 Teflo Filter. 2003. Manufactured by Pall Life Sciences Laboratory Filtration and 

Separation Catalog. pp.30-3l. 

8 REO-7. Manufactured by Cooper Environmenral Services, LLC. Portland, OR. 

www.coopercnvironmeotal.co•n. 

9 Agilent Dryer. Manufacturered by Agilent technologic. Found on the web at: 

http://www.cbem.agilcnt.com 

l l/29f2003 l (or X•1.CEMS SOP VI Page 17 of 17 

VES009436 
VES009437 .pdf 
Appendix C 

Hydrogen Chloride (HCL) Continuous Emission 

Monitoring System Supporting Documents 

Version 1.0 

November, 2·005 

VES009437 
Table of Con toots 

I. Perfonnance Specification Z: Specifications and Test Procedures For Hydrogen 

Chloride (HCL} Continuous Emission Monitoring Systems At Stationary Sources, 

Eli LiUy, November 2005. 

2. Procedure DD: Quulity Control and Quality Assurance Requirements for 

Hydrogen Chloride (HCL) Continuous Emission Monitoring Systems At 

Stationary Sources, Eli Lilly, November 2005. 

VE$009438 
VES009439.pdf 
Appendix D 

Miscellaneous Performance Specifications and Quality 

Assurance Procedures Supporting Documents 

Version 1.0 

November, 2005 

VES009439 
Table of Conte.n«s 

I. Perfonnance Specification 2- Specifications and T&-t Procedures for S02 and NOx 

Continuous Emission Monitoring Systems in Stationary Sources, 40 CT'R 60 

Appendix B, February 2000. 

2. Perfonnance Specification 4A - Specifications and Test Procedures for Carbon 

Monoxide Continuous Emission Monitoring Systems in Stationary Sources, 40 CFR 

60 Appendix B, February 2000. 

3. Performance Specification 4B- Specifications and Test Procedures for Carbon 

Monoxide and Oxygen Continuous Emission Monitoring Systems in Stationary 

Sources, 40 CFR 60 Appendix B, September 30, 1999. 

4. Appendix to Subpart EEE of Part 63 - Quality Assurance Procedures for Continuous 

Emissions Monitors Used for Hazardous Waste Combtl~tors, 40 CFR 63 Subpart 

BEE. September 30, 1999 

VES009440 
VES009441 .pdf 
VES009441 
PERFORMANCE SPECIFICATION Z: 

SPECIFICATIONS AND TEST PROCEDURES FOR 

HCI CONTINUOUS EMISSION MONITORING 

SYSTEMS AT STATIONARY SOURCES 

Revision 1.0 

November, 2005 

VES009442 
EXECUTIVE SUMMARY 

This periormance specification describes the criteria that a hydrodlloric acid (HCI) confinuous 

emission monitoring system (CEMS) must meet to be considered valid for EPA compliance and/or 

other regulata<y applicaUons. Each HCI CEMS must meet the criteria for accuracy. slability, and 

lnslrumental respOnse laid out In this document. In addition, each HCI CEMS must meet the 

installation requirements In PS-Z. 

VES009443 
TABLE OF CONTENTS 

1.0 USING PERFORMANCE SPECIFICATION Z ....................................................................... 3 

1.1 WHAT IS THE PURPOSE AND APPLICABILITY OF PERFORMANCE 

SPECIFICATION Z? ................................................................ ....................................... 3 

12 WHAT WILL BE DISCUSSED IN PS-Z? ......................................................................... 3 

1.3 WHAT ARE THE INSTALLATION AND PRE-PERFORMANCE 

SPECIFICATION TEST REQUIREMENTS? ................................................................... 4 

1.4 WHAT SPECIAL DEFINITIONS APPLY TO P5-Z? ........................................................ 5 

2.0 INTERFERENCES, SAFETY, AND EQUIPMENT REQUIREME.NTS .................................. 8 

2.1 WHAT DO I NEED TO KNOW TO ENSURE THE SAFETY OF PERSONS 

USING PS·Z? .................................................................................................................. 8 

2.2 WHAT EQUIPMENT AND SUPPLIES DO I NEED? ....................................................... 8 

2.3 WHAT REGENTS AND STANDARDS DO I NEED? ...................................................... 9 

3.0 PERFORMANCE EVALUATION PROCEDURES AND REPORTING ................................ 10 

3.1 WHAT IS THE PURPOSE OF THE PERFORMANCE SPECIFICATION 

TESTS AND WHAT IS REQUIRED TO PERFORM THE TESTS? .............................. 10 

3.2 HOW DO I REPORT THE RESULTS OF THE INITIAL PERFORMANCE 

SPECIFICATION TEST? ............................................................................................... 13 

4.0 PERFORMANCE CRITERIA AND CALCULATIONS .......................................................... 15 

4.1 WHAT ARE THE PERFORMANCE CRITERIA FOR MY HCI CEMS? ......................... 15 

4.2 WHAT CALCULATIONS. EQUATIONS, AND DATA ANALYSES ARE 

NEEDED? ...................................................................................................................... 16 

5.0 OTHER REQUIREMENTS AND INFORMATION ................................................................ 23 

5.1 WHAT QUALITY CONTROL MEASURES ARE REQUIRED? ..................................... 23 

5.2 WHAT CAL.IBRATION AND STANDARDIZATION PROCEDURES MUST I 

PERFORM? ................................................................................................................... 23 

5.3 WHAT POLLUTION PREVENTION PROCEDURES MUST I FOLLOW? 

(RESERVEDj ................................................................................................................. 23 

5.4 WHAT REFERENCE TABLES AND FIGURES ARE RELEVANT TOPS· 

YY? .................................................................... ERROR I BOOKMARK NOT DEFINED. 

6.0 RELEVANT REFERENCES ................................................................................................. 26 

Table 1. Performance Speaftcatloo Test Calibration Gas Ranges 

Figure 1. Dynamic Spiking Overview 

jj 

VES009444 
1.0 USING PERFORMANCE SPECIFICATION Z 

1.1 WHAT IS THE PURPOSE AND APPLICABILITY OF PERFORMANCE SPECIFICATION Z? 

The purpose of Performance Specification Z (PS-Z) Is to establish the Initial parformance requirements for 

evaluating the acceptability of a HCI CEMS. Such applications may include, (1) Instrument. method or 

procedure calibration, and (2) evaluation or certification for lnKial acceptance. 

1.1.1 Application 

This specification is for evaluating the acceptabftity of a HCI CEMS at the time of Installation and during 

pariocfic quality assurance checks. PS-Z applies to you if you win be using a HCI CEMS to demonstrnte 

compliance wi1h a regulatory HCI or HCIICI2 emission standard. 

1.1.2 Measurement Capabilities 

The HCI CEMS musl be capable of measuring HCI ooncentrntions In the units of the applicable slandard 

or in units that can be converted to units or the applicable standard. 

1.1.3 Other Monitoring 

If your HCI CEMS Is capable of reporting the HCI concentration In the units of the existing regulation, no 

additional monitoring Is necessary. If your HCI CEMS does not report concentrntions, In the unKs of the 

existing standard. than other monitoring (e.g., oxygen. temperature, and pressure) are necessary to 

convert the units repcrted by your CEMS to the units of the standard. 

1.2 WHAT WILL BE DISCUSSED IN PS-Z? 

PS-Z covers two basic topics: (1) the instrument requirements for an HCI CEMS and (2) the requirements 

that each HCI CEMS must meet during the performance specifiCation test. 

1.2.1 Instrument Requirements 

The HCI CEMS must be able to accurately report concentrations of HCI in stack effluent. II may do so by 

extracting a representative sample (path or point sampling may be used if tha sample Is representative) of 

stack effluent and analyzing the effluent to provide an output proportional to the HCI concentrntion. The 

CEMS operating range (zero to span) should encompass the response of 111e HCI CEMS for all expeded 

HCI oonceotrations, lncludillg the applicable emission llmiL The CEMS must have a system response 

time that is less than or equal to two minutes. Finally, the instrument or operator must be able to perform 

daily calibration drift tests, quarterty calibration error tests, and annual accuracy tests. 

3 

VES009445 
1.2.2 Performance Spe<:lficatlon Tut 

The purpose of the performance specifiCation test is to establish the accuracy. precision, bias, and 

system response time of the HCI CEMS. Spedllcally, the following will be either tesled or doCumented as 

part of the perfomlance specification test requirements listed In Sections 3.0 and 4.0 of this document (1) 

data recorder scale, (2) daily callbralion drill, (3) installation and measurement location, (4) calibration 

drift test (5) calibrallon etTOr lest (6) system response time, (7) slralificallon test, (8) ace<Jracy 

determination. 

1.3 WHAT ARE THE INSTALLATION AND PRE-PERFORMANCE SPECIFlCA110N TEST 

REQUIREMENTS? 

1.3.1 Installation Requlrementa 

The sampDng location of the HCI CEMS shoUld be downstream of all pollution control equipment at a 

position where the HCI concentretion is dlrecUy representative or can be corrected so as to be 

representative of total emissions from the stationary SOUI'Ce. It is recommended that the sampling 

location be at least two equivalent diameters downstream of the nearest control delltces, point of pollution 

generation, bend, or other point at which a change in pollutant concentration or flow disturbance may 

oce<Jr. The sampling location is also recommended to be at least a half equivalent diameter upstream 

from the exhaust or control device. The equivalent diameter Is calculated according 40 CFR Part 60, 

Appendix A, MethOd 1, Section 2.11

• 

E~ er point or path sampling may be used. For point sampling the measuremenl point shoUld be no less 

than 1.0 meter from the stack or duct wall or located over the centroidal area ol the slack or duct aoss 

section. For a path sampling CEMS the effective measurement path should be (1) totally within the inner 

area bounded by a line 1.0 meter from the stack or duct wan, or (2) have at teasl 70 percent of the path 

within the Inner 50 percent of the stack diameter or duct cross section, or (3) be centrally located over any 

part of the centroidal area. 

The sample collection and instrumental analyzer portions ol your HCl CEMS may be located any distance 

from the sampling point provided the transmission efficiency from the sampling point to the sample 

collection point can be determined and meets tha criteria ouUined later In this performance specification. 

It Is also recommended that the sampling probe for the HCl CEMS be located at point without 

stratifiCation (section 3.1.5). 

4 

VES009446 
1.3.2 Reference Method Measurement Location 

You must select, as appropriate, an accessible reference metho<l (RM) measurement point at least two 

equivalent diameters downstream from the nearest control device, the point of pollutant generation, or 

other point at which a change In the pollutant concentration or emission rate may occur, and at least a 

half equivalent diameter upstream from the effluent exhaust or control device. When pollutant 

concentration changes are due solely to d~uent leakage (e.g., air heater leakages) and po[lutants and 

diluents are simultaneously measured at the same location, a half diameter may be used in lieu of two 

equivalent diameters. The CEMS and RM locations need not be the same. If dynamic spiking is 

employed to determine the system accuracy, bias, and precision, the spiking of the calibration gas must 

encompass the sampling system of the HCL CEMS. 

1.3.2.1 Reference Method Traverse Points 

Seled traverse points that assure acquisition of representative samples over the stack or duct crosssection. The minimum requirements are es follOWs: Establish a "measurement line" that passes throogh 

the centroidal area and in the direction of any expected stratification. If this line interferes with the CEMS 

measurements. displace the line up to 30 em (12 ln.) (or 5 percent of the equivalent diameter ol the cross 

section, whichelfe( is less) from the centroldat area. Locate three traverse poiniS at 16.7, 50.0, and 83.3 

percent of the measurement Hne. If the measurement line Is longer than 2.4 meters (7.8 ft) and pollutant 

stratification is not expected, the three traverse points may be located on the tine at 0.4, 1 .2. and 2.0 

meter,; from the stack or duct wall. This option must not be used after wet scrubbers or at points where 

two streams wHh different pollulant concentrations are combined. 

Other traverse points may be selected, provided that they can be shown to the satisfaction of the 

Administrator to provide a representative sample over the stack or duct cr06S section. Conduct all 

necessary RM tests within 3 em (1.2 in.) of the traverse points, but no doser than 3 em (1.2 in.) to the 

stack or duct wall. 

1.4 WHAT SPECIAL DEFINITIONS APPLY TO PS-Z? 

Calibration Drift: The difference in the CEMS output readings from the established reference value after 

a stated period of operation during which no unscheduled maintenance or adjustment took place. 

Calibration Error: The mean difference between the concentration indicated by the CEMS and the 

known concentration gooerated by a calibration source at three levels wtlen the entire CEMS, Including 

the sampling interface is challenged. A CE test Is performed to document the accuracy and linearity of 

the CEMS over the entire measurement range. 

5 

VES009447 
CentroldaJ Area: means a concentric area that is geometrically similar to the stack or duct cross section 

and Is no greater than 1 percent~ the stack Of duct cross-sectional area. 

Continuous Emission Monitoring System: means the total equipment required fOf the determination of 

a gas concentration Of emission rate. The sample Interlace, pollutant analyzer, diluent anal)l2er, and data 

recorder are the major subsystems of the CEMS. 

Correlation Coefficient: determines the extent of a finear relationship between two fields over a given 

period of Ume. 

Data Recorder: The portion of the CEMS that provides a record ol analyzer output, nags which Indicate 

normal operation, and ftags indicating abnormal operation. The data recorder may record other pertinent 

data such as effluent ftow rates, and various Instrument temperatures. 

Diluent Analyzer: means that portion of the CEMS that senses the diluent gas (i.e. 0,) and generates an 

output proportional to the gas concentration. 

Dynamic Spiking: a procedure used to document the accuracy, precision, and bias of the monitoring 

system by quantitatively spiking a certified gas Into the pollutant gas stream. 

Hlgh·level drift: means the absolute difference between a high-level calibration gas and the monitOf 

response. in unijs of the applicable standard. 

Instrument Measurement Range: The range of HCI concentrations the instrument can reliably measure 

from the lowest ooncentration to the highest. 

lnte~pt: va ue~ the Y variable when the X variable is equal to zero. 

Linear Regression: e methodology used lo flnd a formula that can be used to relate two variables that 

are llnea~y related. 

Path Sampling CEMS: A CEMS that samples the source effluent along a path greater than 10 percent of 

the equivalent diameter of the stack Of duct cross section. 

Point Sampling CEMS: A CEMS that samples the source effluent at a single poinl 

6 

VES009448 
Pollutant Analyzer. means that portion of the CEMS that senses the poiiUianl gas and generates an 

output proportional to tho gas concentration. 

Relative Accuracy (RA): means the absolute mean difference between the gas concentration or 

emission rate determined by the CEMS and the value determined by the Reference Method (RM), plus 

the 2.5 peroent error confidence coefficient of a senes of tests. divided by the mean of the RM tests or the 

applicable emission limk. 

Response n me: The time interval between the start of a step change in the system input and when the 

pollutant analyzer output reached 95% of the final value. 

Sample Interface: The portion of the CEMS used for one or more of the following: sample acq<Jis~ion, 

sample transport, sample conditioning, or protection of the monitor from the effects of stack gas. 

Slope: The rate of change of Y relaUve to the change in X. 

Stratification: means the change In effluent concentration in a duct, over time when comparing a 

reference measurement (centroid of duct) to traversed sampllng concentrations. 

Zero drift means the absolute difference between a higt>-level calibration gas and the monitor response, 

In uni1S of the appficab!e standard. 

7 

VES009449 
2.0 INTERFERENCES, SAFETY, AND EQUIPMENT REQUIREMENTS 

2.1 WHAT DO I NEED TO KNOW TO ENSURE THE SAFETY OF PERSONS USING P5-Z? 

People using PS·Z may be exposed to haZardous material, ()!lef8tional hazards, and hazardous site 

conditions. PS-Z does not address all the safety Issues associated with ~s use. It is your responsibility to 

ensure the safely or persons using PS·Z. Some helpful references may include the CEMS manual. tha 

CEMS manufacturer, other reference methods, and oo-s e safety regulations. 

2.2 WHAT EQUIPMENT AND SUPPLIES DO I NEED? 

2.2.1 Equipment for the CEMS 

1. Sample Extraction System: This portion of the CEMS must present a sample of source 

effluent to the sampling module that is direcdy representallva or can be corrected so as to be 

representative of source. Tha sample extraction system lyplcally consists or a sample probe 

and a heated umbilical line. 

2. Pressure Regulation Module: Tha pressure regulation module is designed to remove both 

free partiwlates and water-soluble aerosols from dhe gas stream prior to analysis by the 

sampling module. This module also provides a sample gas to tha analyzer at a constant 

pressure (optional). 

3. Analysis module: Tha portion of the CEMS that quantitates stack gas concentrations of HCI. 

4. Diluent Module: This portion of the CEMS quantifies stack gas concentrellons or oxygen or 

CO,. For systems with a multi-<:omponent analyzer, the same analyzer quantif18S the 

concentration of all measured anaJytes. 

5. System Con1roller: This porlion of the CEMS provides control of the analyzer, sample 

probe. pressure regulation module and the sample lntertace. 

6. Data recorder: Your HCI CEMS must be able to record HCI concentreflons and Instrument 

status signals (flags). 

2.2.2 Equipment Speciflcat.lons 

The CEMS data recorder output range must Include zero and a high-level value. Tha range of tha data 

recorder and tha measurement range of the HCI CEMS will De documented. Tha high-level value is 

chosen by tha source owner or operator and Is defined as follows: 

8 

VES009450 
For an HCI CEMS inslalled to measure contmlled emissioos or emissions lhat are in C<Jmpliaoce with an 

applicable regulation, the high-level value should be at least 1.5 times the emission standard level and 

encompass lhe HCI conoentralion levels expected by the process. 

The CEMS design should also allow the determination of calibration drift at lhe zero and high-level 

values. In special cases, the Administrator may approve a single-point calibration-drift determination. 

2.3 WHAT REGENTS AND STANDARDS DO I NEED? 

2.3.1 Reference Gases, Gas Colis, or Optical Filters 

See Table 1 for reference gas concentration ranges. 

9 

VES009451 
3.0 PERFORMANCE EVALUATION PROCEDURES AND REPORTING 

3.1 WHAT IS THE PURPOSE OF THE PERFORMANCE SPECIFICATION TESTS AND WHAT IS 

REQUIRED TO PERFORM THE TESTS? 

The purpose of !he perfonnance specification tests Is to detennine the accuracy, precision, bias, and 

system response time of the HCI CEMS. 

3.1.1 Protest Preparation 

Prior to the start of yo..- Initial performance specification tests, you must be sure that the HGI CEMS is 

installed according to the specifications laid out in this documenl Alter installing the HCI CEMS, It is 

recommended you use the CEMS for a period of time to ramlilarlze yourself with its operation. It is also 

recommend that you conduct daily cheeks of the zero and high-level drift, conduct a calibration error test, 

and oondud a calibration drift check to verify that the instrument is functJonlng property. When you are 

confident that the lnsln.Jment is performing satisfactorily ~ is time to prepare lor the perfonnance 

specification tests. 

3.1.2 Data Recorder Scale Check 

The range or the data recorder and the measurement range or the HCI GEMS will be documented. The 

CEMS operating range (zero to span) and the range or the data recorder should eocompass both the 

response of the HCl GEMS lor all expected HGt concentrations and the applicable emission Hmll 

3.1.3 Calibration Drift Cheek 

The HCL CEMS must perform a calibration ched< at least once per day. Certified gases must be used to 

perform the zero and high-level drift checks. All data wm ba recorded. 

3.1.4 Installation and Measurement Location Cheek 

The Installation location orthe HCL CEMS must adhere to section 1.3.1 or this document. In addition. the 

location of any reference method testing must adhere to section 1.3.2 of this document. 

3.1.5 Stratification Test 

The stratification test must ba conducted when the facility is operaUng during normal operation. The 

purpose ol this test is to verily that excess stratification of the target poHutant does not exist a the 

sampling point of the monhoring system. 

To detennlne whether effluent stratification exists. a dual probe system should be used to detennine the 

average effluent concentration while measurements at each traverse point are baing made. One probe, 

10 

VES009452 
located at the stad< or duct centroid, Is used as a stationary reference point to indlcaie change in the 

effluent concentration over time. The second probe is used for sampling at lhe traverse points specified 

in Method 1. The traverse points are sampled for five minutes at each point. You may test for 

stratification at lhe HCI CEMS sampling point by using either velocity tests as described in Method t', HCI 

conc<lntrations using Methods 26 or 26A, or an acceptable alternative (i.e. CO or Nox) A minimum of 12 

sampling points will be used, with 6 sampling points along each of the two traverses. 

3.1.6 Seven-day Calibration Drift Test 

The seven-day calibration drift test must be conducted when the facility is operating durtrlQ normal 

operation. The purpose of this test is to verify that the instrument operation Is stable. During the 

calibration drift test period you must determine the magnitude or the zero calibration drift and the high· 

level calibration drift at least once eacih day. During the stability tests no adjustments or calibrations may 

be made to the GEMS. If periodic automatic or manual adjustments are made to the CEMS zero and 

high-level calibration settings. conduct the CD test immediately before these adjustments, or conduct It In 

such a way that 111e CD may also be determiood. 

Tile calibretion drift will be determined at the zero and high-level value ol the HCI CEMS. Introduce to the 

CEMS the reference gases, gas cefis, or optical filters (these need not be certifK!d) for the zero and high 

level values. Record lila GEMS response and subtract lhls value from the reference value. The 

calibration gas concentrations are provided in Table 1. 

3.1.7 Calibration Error 

The HCL CEMS will be challenged three non-consecutive times with zero. mid·level. and high-level 

certified HCL gases (Table 1). The cylinder gases need not be EPA Protocol 1 gases. The calibration 

gases will be injected into the sample system as close to the sampling probe outlet as practical and will 

pass through all CEMS components used during nonnal monitoring. The difference between lhe 

Instrument response and the reference value (certified gas) will be calculated after each injection and the 

resulting three differences will be averaged to determine lhe CE at each measurement point. 

3.1.8 System Response Time 

Introduce zero gas into the analyzer. When the system output has stabilized (no change greater than 1 

percent of full scale for 30 sec), introduce an upscale calibration gas and wa~ for a stable value. Record 

the Ume (upscale response time) required to reach 95 percent of the final stable value. Next, reintroduce 

the zero gas and wah for a stable reading before recordir\Q the response lime (downscale response time). 

Repeal the entire procedure lhree limes and determine lhe mean upscale and downscale response 

limes. The slower or longer of the two means is the system response time. 

11 

VES009453 
Canbration gas ranges lor the response time test are provided in Table 1. II using a multi-component 

analyzer. the response time can be based on any analyte measured by the CEMS. 

3.1.9 CEMS Accuracy 

The accuracy of the HCI CEMS shall be determined by pertonning either a relative accuracy 

determination or by dynamic spiking. 

3.1.9.1 Relative Accuracy (RA) 

Conduct the RA test while the affected facility is operating during normal operation, or as specified in an 

applicable subpart. The RA test may be conducted during the CD test period. 

Reference Methods (RMl. Unless olherwlse specified In an applicable subpart or the regulations, 

Methods 26 or 26A, or their approved alternatives, are the reference methods for HCI. Other reference 

methods for moisture, oxygen, etc. may be necessary. 

Sampfing Strategy lor RM Tests. Conduel the RM tests In SUCh a way tltat they will yield rasulls 

representative of the emissions from the source and can be correlated to the CEMS data. It is preferable 

to conduct the diluent (if applicable), moisture (II needed), and pollutant measurements simultaneously. 

However, diluent and moisture measurements that are taken within an hour of the pollutant 

measurements may be used to calculate dry pollutant concentration and emission rates. In order to 

correlate the CEMS and RM data properly, note the beginning and end of each RM test period of each 

run (Including the e•act time or day) on the CEMS chart recordings or other permanent record of output. 

For Integrated samples make a sample traverse of at least 21 minutes, sampling for an equal time at 

each traverse point. 

Number of RM Tests. Conduct a minimum of nine sets of ell necessary RM test runs. 

NOTE: More than nine sets or RM tests may be performed. II this option Is chosen, a maximum of three 

sets of the test resulls may be rejected so long as the total number of test results used to determine the 

RA Is greater than or equal to nine. However, all data must be reported, including the rejected data. 

Correlation of RM end CEMS Data. Correlate the CEMS and the RM test data as to tlte time and 

duration by r.-st determining from the CEMS final output (the one used for reporting) the Integrated 

average pollutant concentration or emission rate for each pollutant RM lest period. Consider system 

response time, n mportan~ and confirm that the pair of resuHs are on a consistent moisture, temperature, 

and diluent concentration basis. Then, compare each Integrated CEMS value against the corresponding 

average RM value. II the RM has an Integrated sampling technique, make a direct comparison or the RM 

results and CEMS Integrated average value. 

12 

VES009454 
Calculate the mean difference between the RM and CEMS values In the units of the emission standard, 

the standard deviation, the confidence coeffiCient, and the relative accuracy according to the procedures 

In Section 4.0. 

3.1.9.2 Dynamic Spiking 

Dynamic spil<.lng can be used In lieu of the Relative Accuracy determination as an allemalive method for 

documenting the accuracy, pro<:lslon, and bias of the HCI CEMS. Figure 1 provides an overview of the 

dynamic spiking arrangement. Conduct the dynamic spiking test while the affected facility Is operating 

during nonnal operation. 

While the HCI CEMS Is sampling flue gas, HCI standard gas Is introduced Into the HC1 CEMS sample 

Interface by using a mass now oontroller (or equivalent device). The target ratio of actual flue gas to the 

HCI standard gas Is 9:1, but must be kept at a minimum ratio of 1 :1. The HCI ooncenttation is quantitated 

by the HCI CEMS. One minute averaged values, in units of ppm corrected to dryness and 7% oxygen, are 

collected. All data should be archived. 

An element of opportunity shall be used to calculate the dilution of the dynamically spiked HC1 reference 

gas (represents the actual HCL reference gas concentration). The element of opportunity is an analyle, 

which would normally be present in the flue gas at steady concentrations. Examples of prospective 

elements of opportunity would be 0,, NOx, SO,, CO,, or moisture. This anelyle is measured. 

downslteam of the HCL CEMS, using a certified reference CEMS. 

In acldltlon, a calibrated Laminar Flow Element (flow as an element of opportunity) can be used as a 

secondary indicator for calculating the dynamically spiked HCI concentration (represents the reference 

HCI concentration). Whie the Laminar FlOw Element Is mainly for verification of the dynamic spiking 

system operation, the use of flow as an element of opportunity can be used to calculate the concentration 

of the HCI dynamic spike. 

In addition, the t>aseline HCI concentration (normal HCL concentration of !tie stac1< effluent without HCL 

spiking) shall ba determined. The l>ase!ine HCI concentration is t>ased upon a series of 10, one-minute 

averaged data points. Baseline dala must be collected immediately prior to each test run. The data 

points must include the HCI concentration, element of opportunity ooncentration(s) and the llow recorded 

by the laminar flow element. II is recommended that a sHe·specific standard operating procedure, for the 

dynamic spiking exercise, be prepared and used as guidance for the dynamic spiking accuracy test 

3.2 HOW 00 I REPORT THE RESULTS OF THE INmAL PERFORMANCE SPECIFICATION TEST? 

13 

VES009455 
Summarize the resuks of the calibration drift. calibration error, response time, stratification, and accuracy 

tests in tabular loon. Include all data sheels. calculations. and records of CEMS measurements 

necessary to substantiate the performanoe of the CEMS and any other devices or methods (e.g .. method 

26A). The CEMS measurements shall be reported to the agency in units of ppmv. on a dry basis. 

14 

VES009456 
4.0 PERFORMANCE CRITERIA AND CALCULATIONS 

4.1 WHAT ARE THE PERFORMANCE CRITERIA FOR MY HCI CEMS? 

You must demonstrale that your HCI CEMS has adequate precision, accuracy, system response time and 

dala reporting capabilities to determine if your facllay Is In compliance with HCl emission standards or 

operating permn limits as specified In applicable regulations or permits. You will demonstrate this 

capacity by showing that your HCI CEMS meets the following performance criteria. 

4.1.1 Data Reeonler Seale 

The measurement range of the HCL CEMS, and the dala recorder scale, roost encompass the expected 

HCL concentrations as wei as the applicable emission limit. 

4.1.2 Calibration Drift 

The dally zero and hlgh~evel calibration drift is 5% of the Instrument span. Zero and high-level calibration 

drifts shall be adjusted, at a minimum, whenever the 24-hour zero drift exceeds the limits of the 

calibration drift specification. The amount of excess zero and hlgh~evel drift measured at the 24-hour 

interval checks will be recorded. Section 4.2 provides the equations for calculating the zero and high· 

level calibration drills. 

4.1.3 Installation and Measurement location 

The installation requirements and measurement location of the HCL CEMS will meet the specifications 

ouUined in section 3.1.1 and 3.1.2 of this document 

4.1 .4 Stratification Test 

The stratification in the slack or duel, at the measurement location, must be less than or equal to a 10 

pen;ent between lhe average concentration In the duct or slack and the concentration at any point more 

than 1.0 meter form the duct or stack walt. Section 4.2.2 provides the equation for calculating the 

stratification of the slack or duct. 

4.1.5 Seven-day Calibration Drift Test Criteria 

The dally zero and high-level drift each must be less than 5% of the Instrument span for seven 

consecutive days. See Section 4.2.2 for the equations used to determine the zero and high-level drift. 

15 

VES009457 
4.1.6 Calibration Error Test 

The mean difference between the CEMS and the reference values, at all three test levels, must be no 

greater than 5% of span. See Section 42.3 lor the equation used to determine the calibration error. 

4.1.7 Response Time Test 

The CEMS response time shall not exceed 2.0 min to achieve 95 percent of the final stable value. II 

using a multi-component analyzer, the response time can be based on any analyte measured by the 

CEMS. 

4.1.8 Relative Accuracy 

Tha RA ol the CEMS must not be greater than 20% of the mean value olthe reference method (RM) test 

data, or not greater than 10% in terms ol the emission standard (ppmv, dry), or have an absolute 

difference of lass than 5 ppmv between the mean reference value and the mean CEMS value. See 

Section 4.2.5 lor the equations used to determine the relaUve aocuracy of your CEMS. 

4.1.9 Dynamic Spiking 

Dynamically spiking may be used in lieu of a relative accuracy test as a means to document the accuracy, 

precision, and bias of the HCI CEMS. 

The criteria lor the HCI dynamic spiking is: 

• The correlation coefficient r, must be greater than 0< equal to 0.90 

• The slope must be 1.0, +/- 0.15 

• The Intercept must be equal to or less than 15% of the Instrument span. 

See Section 4.2.8 lor equations to determine the linear correlation coefficient, the slope and the Intercept 

At a minimum, the data set must meet the correlation coefficient. If thls Is not met, the dynamic spiking 

procedure must be repeated until the correlation coefficient criteria is met. If the HCI CEMS has mel the 

correlation coefficient requirement, but does not meet either the slope, or intercept c:rltaria, a bias exists 

and a correction factor must be applied to the HCI CEMS for data collection. The equations to determine 

the corrected value are provided in SectiOn 4.2.6.1. The correction factor must be applied to the HCI 

CEMS one-minute average data until a new dynamic spiking procedure Indicates the specific bias no 

longer exlsts, or, a different correction factor (bias) is indicated. 

4.2 WHAT CALCULATIONS, EQUATIONS, AND DATA ANALYSES ARE NEEDED? 

16 

VES009458 
4.2.1 Arfthmetlc Mean 

Calculate the arithmetic mean of a data set as follows: 

-

X=-I "" £...XI 

n 

(Equation 1) 

where: 

X = Arithmetic mean 

n = Number of data points 

"' = Value or each data point 

4.2.2 Daily Upscale and Zero Drift 

CD =(IR -Ail S) ' 100 (Equation 2) 

where: 

CD = Percent calibration drift (% ). 

R = Reference value of zero or high level calibration gas introducecl lnto the 

monitoring system (ppmv). 

A = Actual monitor response to calibration gas (ppmv), 

S = Span of the instrument (ppmv). 

4.2.3 Calibration Error 

CE = !<1,,.1 S l • tOO (Equation 3) 

where: 

CE = Percent calibration error(%). 

d.., = Mean difference between CEMS response and the known reference gas (ppmv). 

S = Span of the monitor (ppmv). 

17 

VES009459 
4.2.4 Moan Difference 

Calculate the arithmecic mean difference as follows: 

{Equation 4) 

where : 

ds11o = Arithmetic mean of differences 

n = Number of data sets 

di = difference of each da18 set 

And 

d. =xr- yr {Equation 5) 

where: 

= Value at data set x 

Value at data set y 

4.2.5 Relative Accuracy 

The RA lor the monitors will be calculated using the least restrictive of equation 6 or equation 7: 

RA = {ld.,.l + ICCIJ {Equation 6) 

or 

RA = {(id.,.I + ICCI)tTM.,.)"100 {Equation 7) 

where: 

RA = Relative accuracy, either percent or ppmv or % absolute, 

d.,. = Arithmetic mean of differences between value measured by the installed CEMS and the 

reference method, 

CC = Confidence coeff'&clent, 

18 

VES009460 
TM.,. • Average value measured by the reference test method monKors. 

4.2.6 Confidence Coefficient 

The confidence coefficient will be calculated using equadon 8: 

CC = lo.

9,. • (S.I (n")) (Equation 8) 

where: 

CC = Confidence coefficient, 

to..n = t-value obtained from Table 2. 1 in Performance Specification 2, 40 CFR Part 60 

Appendix B 

4.2.7 Standard Deviation (of Differences) 

S. = Standard deviation of differences measured between the irlSiaOed CEMS and the 

reference methods cal<:ulated using equation 8: 

(Equation 9) 

where: n = Number of values In this data sel 

4.2.8 Dynamic Spiking 

To determine the reference value of HCL during a dynamic spiking run: 

Opp - post.,,, · HC1 .., = I - • Ca/Gas + BaselineHCI 

Opp - pre.,, 

(Equation 1 0) 

Where: 

HCI ,.. = Reference HCI value for run "X' 

Opp-post,.. = average reference element of opportunity value during test (downstream of spike) 

Opp-pre"" =average reference element of opportunity value during test (upstream of spike) 

19 

VES009461 
CaiGas ~ HCI calibration gas coocentratlon 

Baseline HCI " CEMS HCI average baseline value 

Using data from each of the three test runs, perfonn a linear regressioo of the CEMS HCI average values 

against the Reference HCl values using the following equations given below: 

(Equation 11) 

where: 

The y intercept 

= The slope 

The intercept is calculated according to lhe following equation: 

(Equation 12) 

where: 

I • J= - I y, II l.t 

The slope or the line is calculated according to equation below: 

• L (x,-x){y,- Ji) 

b, =~-~~-------- " (Equation 13) 

L:(x, - x)' ,., 

The linear correlation coefficient is calculated according to the follOwing equation. 

20 

VES009462 
(i: (x, - .f)(y, -n)' l l •l 

,. -. " })x, -x( [ (y, - .W 

(Equation 14) 

,... 1=-1 

4.2.8.1 Dynamic Spiking Corrected Values 

If the HCI CEMS fails to meet both the stope and intercept criteria. the following correction factor must be 

applied to the on&-minute average HCI data: 

(Equat.lon 15) 

Where: 

cc = corrected CEMS HCL ooneentration 

y1 = CEMS reported HCL concentration 

bo = the intercept of the least squares linear regression line 

= the stope of the least squares linear regression line 

b). If the HCI CEMS fails to meet the stope criteria, but meets the intercept criteria, the following 

correction factor must be applied to the onEHllinute average HCI data: 

(Equatlon 16) 

c). If the HCI CEMS tails to meet the Intercept criteria, but meets the slope criteria, the following correction 

factor must be applied to the o~m nu e average HCI data: 

(Equation 17) 

21 

VES009463 
4.2.9 Stratification 

The value at each traverse point are then compared to lhe average value for all sampling points to 

determine the peroent stratification using the following equation: 

S "'IC--I C (ll'f: i•tOO% (Equation 18) 

where: 

S c percent stratification 

c, = concentration or velocity at sampling point I 

C.,.. ., average concentration or velocity at all sampling points 

22 

VES009464 
5.0 OTHER REQUIREMENTS AND INFORMATION 

5.1 WHAT QUAUTY CONTROL MEASURES ARE REQUIRED? 

Ongoing quality control will include daily calibration drift tests, quarterly calibration error audijs (absolute 

calibraUon audit), and annual accuracy test audits. SpecifiC procedures and performance criteria are 

included In Procedure DD: Quality Control and Quality Assurance Requirements for Hydrochloric Acid 

Continuous Emission Monitoring Systems at Stationary Souroes. 

5.2 WHAT CALIBRATION AND STANDARDIZATION PROCEDURES MUST I PERFORM? 

Refer to your CEMS owner's manual and manufacturer to determine what calibration and standardization 

procedures are required for your HCI CEMS. 

5.3 WHAT POLLUTION PREVENTION PROCEDURES MUST I FOLLOW? (RESERVED) 

23 

VES009465 
Table 1. Performance Specification Test Calibration Gas Ranges 

HCI Calibration Gas Concentrations ' 

Test Units Zero Mid.t.evel High-Level 

Calibration Drift and %of Span 0-30 NA 50-100 

Response Time Test • 

Calibrallon Error Test %of Span 0-30 30-50 50-100 

Dynamic Spiking %of Span 0-50 25-75 50-1 00 

'A copy of the supplier's certificate of analysis must be provided lor each gas cylinder. Calibration gases 

do not need to be Protocol 1 gases. 

"If conducting the response Ume using a mulll-romponent analyzer, the response time test can be based 

on any measured analyte. 

24 

VES009466 
Figure 1. Dynamic Spiking Apparatus 

Dynamic Spiking Apparatus 

So pie Probe Heated line inside 

sample umbillical 

Hoole umpl•lln• 

lueGas 

l 

•Heated Filter 

• Pruaure Control 

•Laminar Flow 

Element 

HCL 

CEMS 

Calibntion Manifold 

(Mass now met""') 

900·1000 ppm HCL In N2 

On Reference 

CondiUontt Manurement(5) 

25 

VES009467 
6.0 RELEVANT REFERENCES 

I. United States. Environmental Protection Agency [EPA). Technology Transfer NetW()(k. Emission 

Measurement Center. Promulgated Methods. Method 1: Sample and Velocity Traverses for 

Stationary Sources. Washington, DC: EPA; 2004. Available: 

hltp:l/www.epa.gov/llntemtlpromgatelm-01.pdf via the Internet. 

11. United States. Environmental Protection Agency [EPA). Technology Transfer Network. 

Emission Measurement Center. Promulgated Methods. Method 2: Determination of Stack Gas 

Velocity and Volumetric Aow Rate. Washington, D.C: EPA; 2004. Avaiable: 

hllpJiwww.epa.gov/Hnlemclpromgate/m-02 pdf via the lntemeL 

111. United States. Environmental Protection Agency (EPA). Technology Transfer Networ1<. Emission 

Measurement Center. Performance Specifications. Perfonnance Specification 2· Specifications 

and Test Procedures for S02 and NOx Continuous Emission Monitoring Systems in Stationary 

Sources, 40 CFR 60 Appendix B, February 2000. Available: 

http://www.epa.gov/llntemtlperfspec.html via the Internet. 

IV. United States. Environmental Protection Agency (EPA). Technology Transfer Network. Emission 

Measurement Center. Performance Specifications. Performance Specification 4A -

Specifications and Test Procedures for Carbon Monoxide Continuous Emission Monitoring 

Systems ln Stationary Sources, 40 CFR 60 Appendix B, February 2000. Available: 

http·l/www epa.gov/Hn/emtlperfspec.html via the lntemel 

V. United Stales. En•ironmental PrO(ection Agency (EPA). Technology Transfer Nelwotk. Emission 

Measurement Center. Performence Specifications. Performance Specification 46 • 

Specifications and Test Procedures for Carbon Monoxide and Oxygen Continuous Emission 

Monitoring Systems in Stationary Sources, 40 CFR 60 Appendix B, September 30. 1999. 

Available: http://www.epa.govltln/emc/perfspec.html via the tntemel 

26 

VES009468 
VES009469.pdf 
Method 301 Evaluation of Candidate Conditional 

Methods 

X-Ray Based Filter Method (XFM) 

Multi-Metals Instrumental Analyzer Procedure 

(Xact-IAP) 

Quantitative Reference Aerosol Generator (QAG) 

Prepared by: 

Cooper Environmental Services, LLC 

101 80 SW Nimbus Blvd Suite J6 

Pot11aod, Oregon 97223 

Revision 1.0 

June, 2005 

VES009469 
VES009470 
Executive Summary 

A new metal emissions measurement and validation system has recently been developed that 

has the potential to significantly improve our understanding of meta.l emissions from a wide 

mnge of source categories. This system consists of: 

• A continuous emission monitoring system (Xact-CEMS) 

• An instrumental analyzer procedure (Xact-IAP) 

• A sampling and analysis mcasu rernetJt method (XFM) 

• A NlST-traceable reference aerosol generator (QAG) 

The measurement components of this system are based on collecting a representative sample 

of stack gas on a chemically reactive filter (solid sorbent) that traps both particulate and 

vapor phases of metals, followed by non-desuuctive X-ray fluorescence (XRF) analysis 

using procedures consistent with ambient measurements. This system is applicable to 

elements with atomic number ronging from 13 (AI) to 92 (U), and can measure Be after nondestructive XRF analysis if other analytical procedures are used; it can provide detcMion 

limits as low as 0.1 rg/dscm with 15 minute turn around times or lower detcclion limits with 

longer sampling and analysis times; and has demonstrated accuracies better than five percent 

and precisions better than three percent. These generation and measurement components are 

independently traceable to NIST: the QAO thr·ough procedural traceability and solution 

standards, while the measurement metbods are analytically traceable tluough thin film 

standards and NJST standard reference materials. 

A series of laboratory and field tests have been conducted to demonstrate that the QAG, 

XFM and Xact-IAP components of this new system meet Method 30 I accurucy and precision 

requirements for conditional method status. Each of the methods met the performance 

criteria outlined in the Method 30 I test plan. These criteria included the following: 

• Filter natlos- percent of Cr and Pb trapped on the XFM front PTFE mrer. Although 

this criterion is not required by Method 301, high percentages assure high particle 

trapping efficiency. 

• Metal ratios - ratio of Pb-nonnalized solution concentration to Pb-normalized 

aerosol concentration. This criterion is also not required by Method 301 1 but ratios 

close to one assure high relative generation, tTllDSport and sampling efficiencies for all 

metals including vapors. 

• Efficiency - percent ofNJST-traceable reference aerosol concentration measured. A 

high percentage assures high absolute generation, transport and sampling efficiencies. 

• Bias corr ectlon factor - rotio of reference to measured aerosol concentration. A 

value close to one indicates high method accuracy. 

• Pr ecision - percent relative standard deviation determined from sequential 

measurements. A low percent value indicates a highly precise and stable system. 

• Linearity - correlation coefiicient (r) based on a regression analysis of a plot of 

measured versus reference aerosol concentration. 

Melhod301 E\'al.: VI.O Page i ofxii 

VES009471 
These criteria and their acceptance values are based primarily on those in Method 301 and 

were defined in the 301 validation test plan (Appendix A). DUI'ing these tests, five elements 

(As, Cd, Cr, Pb. and Hg) were spiked at concentrations ranging from blank to about 120 

11gldscm. All three (QAG. XFM, and Xact-IAP) independent approaches showed good 

agreement over this wide range of concentrations, and all three methods met the required 

criteria for all five metals. These results are summarized in the following three tables for the 

QAG reference aerosol generator, and the XFM and Xact-IAP measurement approaches. 

The Xact-IAP table includes results from all 192 Xact-IAP runs. 

Comparison of QAG laboratory results with criteria acceptance values. 

Criteria 

No. Runs 

Filter Ratio (% Front) 

Metal Ratio (SoiJAer.) 

Efficiency(%) 

Predslon (%) 

Uneanty- C«r. Coer. { r) 

Acco table 

>9 

>98 

0.9- 1.1 

>80 

<10 

>0.85 

'XFW •od Xad resub bf,. the N!Ms. 

"Confii"TTWCC \Jiill'l hlepetV:lent tCP INif')W NtiJIS 

Results' Met Criteria 

>25 Yes 

>99 Yes 

0.95. 1.01 Yes• 

94- 100 Yes 

<4 Yes 

>0.99 Yes 

Comparison of XFM field test· r esults with criteria acceptance values. 

Criteria 

No. Runs 

Bias Corr. Factor 

Precision (%) 

linearity- Corr. Coef. ( r) 

'Xrlol rt.Uta b' all M ¥cmeniS 

Acce able 

>9 

0.80 . 1.2 

<10 

>0.85 

'Confltmt<l wiCh independen!K::P an:s~PJaa ,..u e~ 

Resutts• 

26 

0.94 . 0.97 

<3 

>0.99 

Mot Crltoria 

Yes 

Yes• 

Yes 

Yes 

Comparison of Xact-IAP field test r esults witb criteria accephmce alu~-s. 

Criteria Acco table Results• Mat Criteria 

No. Runs >9 192 Yes 

Bias Corr. Factor 0.80 -1 .. 2 1.00-1.14 Yes 

Precision (%) <10 <3 Yes 

Linearity - Corr. Coef. ( r ) >0.85 >0.99 Yes 

-x.cz.w,....~« .. filriiJI!>etMtem 

Many more test runs than required by Method 30 I were conducted, and all of the data from 

these runs were included in this evaluation. The QAG and XFM tables shown below include 

results from all 26 XFM runs. 

The filter and metal mtios listed for the QAG are bigh and indicate that the relative 

generation, transport and sampling efficiencies for all elements are within the experimental 

accuracy of I 00%. The efficiency, precision and Linearity values for the QAG are also all 

well within the acceptable range. In the case of the XFM and Xact-IAP measurement 

Method 301 E".J.~ VI.O Page ii of xii 

VES009472 
methods, all of the criteria were met and the values were substantially within the acceptable 

range. which in the case of the bias aod precision were more restrictive in our test plan than 

required by Method 301. The high correlation coefficients indicate highly linea r methods. 

This high degree of linearity is illustrut:cd with the following four representative plots of the 

XFM and Xact-IAP measured values versus the independent QAG reference aerosol 

concentration during laboratory and field tests at a hazardous waste incinerntor. 

15 ~---------------------, 

0 

CADMIUM 

n*26 

y • o.tts• - 0.134 

R2 • 0.915 

50 100 

QAG Cone (IJgldacm) 

150 

50 r---------------------~ 

0 

MERCURY 

•1~ 

y s- O,t71x • 0.542 

R' • O.lt3 

50 100 

QAG Cone g/docm) 

150 

Representative scatter plots of XFM and Xact-L<\P measured concentrations versus 

QAG reference aerosol concentrations during laborator y valldatlon tests of the QAG. 

150 ,-----------------------. 

y• 1.01k · U OS 

R'•t.tt1 

0 

~------50 ------------ 100 --~ 150 

QAG Con<.(lll>'dscm) 

150 .------ ---------, 

Lead 

n:192 

0 

'r • O.tt1x • 1.124 

R' • O .. H2 

so 100 

QAG Cone. (pg/doC0!1) 

150 

Representative scatter plots of XFM and Xact-IAP measured ro cc ntn~tl s versus 

QAG reference aerosol concentrations during field validation tests or the XFM und 

Xact-IAP. 

Tite XFM and Xact-lAP are mgged and robust methods that are applicable to a wide range of 

sources and elements. Because these methods include dilution sampling techniques, they are 

relatively insensitive to most stack gas characteristics (temperature, moisture, PM 

concentration, and chemistry) and can be optimized for specific stack conditions by adjusting 

dilution ratios, sampling times, etc... Their range of applicability has been demonstrated by 

results from these tests as well as other laboratory and field tests over the past five years 

including relative accuracy testing using both Method 2~and Outario HydroJ reference 

methods. Examples of these field validation test results are illustrated with the following two 

figures. The plot of lead shows a strong linear relationship between the Xact and Method 29 

McdlOO 3()L 6val.: VI.O Page iii of xii 

VES009473 
results up to 2,200 llg/dscm and had a relative accuracy of 4%. The mercury plot shows a 

similar strong linear relationship between the XFM and Ontario Hydro reference method 

results at concentrations dow11 to about l llg/dscm and bad a relative accuracy of 1 1%. 

- 2,500 .,..---- ------. E 

:ill 2,000 

8 1,000 

~ 500 

Lead 

n=11 

y a 1.056x • 5. 786 

R2 z 1.000 

~ 1,500 li 

>< oc -~ --...-~---l 

0 500 1,000 1,500 2,000 2.500 

M2ll Cone. {llg/dKm) 

Mercury 

n=9 

• y = 908~ + 0.152 

R' = 0.962 

2 4 

OH Cone. (IJ9/dscm) 

6 

Examples of field validation test r esults at a Dlllnitions incinerator• (left) and at a coalfired utllity boller \\1th baghouse and NO, controls5 (right). 

These tests have included wet and dry incinerators, and wet and dry coal-fired utility boilers 

covering a range of contmls including electrostatic precipitators, scn1bbcrs and NO, catalytic 

reduction controls. The XFM and Xact-lAP are also consistent with mnbieot me:Jliurement 

metbods6

•

7 and applicable to most of tbe elements typically measured ht the ambient 

environment. Thus, the recommended range of source categories for which the XFM and 

Xact-lAP are applicable includes fugitive and dueled emissions such as those from 

hazardous, municipal, sewage and other incinerators; cement and lime kilns; smelters and 

mills; mineral processing, plating and boiler sources using control technologies such as bag 

bouse filtration. electrostatic precipitation, scrubbers and NO, controls. 

Also, this technology offers the following additional advantages: 

• Significantly shorter reporting times (As short as 15 minutes compared to 3 weeks) 

• Precise (<3%), accurate (beuer than 5%), linear (r>0.99) and verifiable results due to 

non-destructive analysis 

• Minimal operator requirements 

• The methods are safe and easy to use and generate no hazardous wa.~te. 

The results from these tests as well as results from previous field tests support the following 

conclusions. 

• The QAG candidate reference aerosol generator is independent of its application, met 

all of the required validation criteria, and should be approved as a NIST-traceable 

reference aerosol generator for compliance and other regulatory applications such as 

initial certification and continuing quality assurance audits of multi-metals CEMS as 

well as calibration and validation of metal measurement methods. 

Page iv of xii 

VES009474 
• The XFM and Xact-IAP candidate conditional methods for measuring metal 

concentrations in emissions from stationary sources met all of the required validation 

criteria; have demonstrated d1eir applicability to a range of source types, controls and 

stack conditions; and should be approved for general compliance and other 

regulatory applications such !lS initial certification and continuing quality nssuranee 

audits of multi-metals CEMS, emission compliance audits, trial bums, and other 

regulatory applications where stack gas metal emission measurements from stationary 

sources are required. 

Mcehod 10 I Enl.: VI .0 Page vofxii 

VES009475 
Table of Contents 

Executive Summary ........ ~ ................................................................ ~ ........... ~ ........................ I 

Appeodlces ............................................................................................................................ viii 

List of Figures ................................ ~ ........................................................................ ~ ............. ix 

List of Abbreviations .......................................................................... ~ ................................. xi 

1.0 Introduction ................................ - ......... ~ ..... ~ ........................................... ~ .................. 1 

What is this report about? ... . ... ....... ... ...... .. . ... .. ... ... .. .. .... . .. .. .. .... ... . . .. ..... ..... ... . ... .... ..... ... .. ... .. I 

Why are we concerned about metal emissions? ................................................................. I 

Why is the current metals measurement system inadequate'/ ............................................. I 

What is this new metals measurement system? .................................................................. 2 

What are these candidate conditional methods? ................................................................. 2 

Why are the XFM and Xact-IAP candidate methods more appropriate than Method 29?. 2 

Why are these methods important to the EPA and other stakeholders? ............................. 3 

How was d1e perfoffilance of these methods evaluated? .................................................... 3 

Where are the results presented in this report'/ ................................................................... 3 

2.0 Approach ... ~ .. ~ .............................................................. - .............................................. 3 

2.1 Overview .................................................................................................................... 3 

2.2 General Approach ...................................................................................................... 4 

2.3 Method Independence ................................................................................................ 5 

2.4 QAG Validation (Phase!) .......................................................................................... 7 

2.5 XFM and Xact-IAP Validation (Phase IT) ............................................................... I I 

2.6 Deviations from Test Plan ....................................................................................... 12 

3.0 Methods ......................................................................................................................... 14 

3.1 QAG Reference Aerosol Generator ......................................................................... 14 

3.2 XFM Candidate Omditional Method ...................................................................... 18 

3.3 Xact lnstrumental Analyzer Procedure .................................................................... 21 

4.0 Calculations .................. ~ ..... ~ ................................................................ ~ ..................... 24 

4.1 Overview .................................................................................................................. 24 

4.2 List of Symbols and Terms ...................................................................................... 24 

4.3 QAG Reference Aerosol Concentration .................................................................. 26 

4.4 XFM Measured Aerosol Concentration ................................................................... 27 

4.5 Xact·IAP Measured Aerosol Concentration ............................................................ 28 

Melbod 301 Eval.: VI.O Page vi of xii 

VES009476 
4.6 Validation Comparison Parameters ......................................................................... 28 

4.7 Other Comparison Parameters ................................................................................. 33 

5.0 Quality Control and Assurance .................................................................................. 35 

5.1 Overview .................................................................................................................. 35 

5.2 QAG ......................................................................................................................... 35 

5.3 XFM ......................................................................................................................... 37 

5.4 Xact-IAP .................................................................................................................. 38 

6.0 Results and Di.scussion ................................................................................................. 40 

6.1 Overview .................................................................................................................. 40 

6.2 QAG Validation ....................................................................................................... 40 

6.3 XFM and Xact-IAP Validation Overview ............................................................... 48 

6.4 XFM Validation ....................................................................................................... 50 

6.5 Xact-IAP Validation ................................................................................................ 52 

7.0 Range of Method Application ..................................................................................... 55 

7.1 Overview .................................................................................................................. 55 

7.2 Criteria for Candidate Method Applicability ........................................................... 56 

7.3 Key Sampling and Analysis Features ...................................................................... 56 

7.4 Key Emission Characteristics .................................................................................. 57 

7.5 Filter Trapping Efficiency for Vapor Phase Metals ................................................. 58 

7.6 Applicable Concentration Range ............................................................................. 62 

7.7 Deposit Stability ....................................................................................................... 62 

7.8 Moisture ................................................................................................................... 63 

7.9 Holding Times ......................................................................................................... 64 

7 .I 0 Applicable Elements ................................................................................................ 65 

7.11 Other Related Tests .................................................................................................. 65 

7.12 Applicable Source Categories .................................................................................. 66 

8.0 Conclusions and Recommendations ........................................................................... 67 

9.0 Glossary ........................................................................................................................ 68 

10.0 References ..................................................................................................................... 73 

Method 301 Eval: VI.O Page vii of xii 

VES009477 
Appendix A: 

Appendix B: 

Appendix C: 

Appendix D: 

Appendix E: 

Appendlx F: 

Appendix G: 

Appendix H: 

Appendix 1: 

Appendix J: 

AppendixK 

Appendix M: 

M¢thod 301 fvnl.: VI.O 

Appendices 

Draft Test Plan for Validating a Reference Procedure for Measuring 

tl1e Concentration of Metals in Eli Lilly and Company's Hazardous 

Waste Incinerator Stack Gas 

Determination of Metal Emissions from Stationary Sources Using 

Filters and Solid Sorbents with X-Ray Fluorescence Analysis 

Standard Operating Procedure for Generating a Quantitative Multi· 

Metals Reference Aerosol with the CES QAG 

Derennination of Metal Concentrations in Emissions from Stationary 

Sources (Instrumental Analyzer Procedure) 

Perfo!TIU\nce Specifications for a Quantitative Reference: Aerosol 

Generator 

Specifications and Test Procedure for X-Ray Fluorescence Based 

Multi-Metals Continuous Emissions Monitoring Systems at Stationary 

Sources 

Quality Assurance Requirements for X-Ray Fluorescence Bused 

Multi-Metals Continuous Emissions Monitoring Systems at Stationary 

Sources 

QA Information during Phase I 

QA lnfonnation during Phase 11 

Phase I Test Data 

Phase U Test Data 

Calculations Used for Method 301 Validation Tests 

Additional Daw in Support of Service and Range Extension of 

Candidate Methods 

Related Reports Produced by Cooper Environmental Services 

Page viii of xii 

VES009478 
List of Figures 

Figure I: Schematic flow diagram illu$trating key aspects of the general validation 

procedure ................................................................................................................................... 5 

Figure 2: Schematic representation of key components ofCES' reference aerosol generation 

system ....................................................................................................................................... 6 

Figure 3: Flow diagram showing tbe experimental arrangement used to validate lbe QAG 

reference aerosol generator ....................................................................................................... 8 

Figure 4: Schematic representation of the experimental arrangement used in Phase i to 

validate the QAG reference aerosol generator .......................................................................... 9 

Figure 5: A. Schematic of flow through QAG components. B. Overview of the set-up of 

QAG components .................................................................................................................... 15 

Figure 6: Schematic flow diagram of the sampling train used in Phase I and [( XFM 

validation tests ........................................................................................................................ 19 

Figure 7: Photogtaph of the a.~scmb ed port adaptor, extraction assembly and filter holder .. 19 

Figure 8: Exploded schematic view ofXFM filter holder with filter cassette ........................ 21 

Figure 9: Overview of Xact-IAI' components and flow schematic ........................................ 23 

Figure 10: QAG solution mass loss rate during Phase !testing ............................................. 36 

Figure 11: QAG solution mass loss rate during Phase 11. .......................•.•......•.•••••..••........••.. 37 

Figure 12: QAG-generated and XFM- and Xact-IAP-measured aerosol concentrations during 

Phase I tests ............................................................................................................................. 41 

Figure 13: Ratio ofXFM and X act-lAP measured metal concentrations to the QAG reference 

aerosol concentration .............................................................................................................. 4 2 

Figure 14: Phase I QAG linearity plots as determined by the XFM ....................................... 46 

Figure 15: Phase I QAG linearity plots as determined with the Xact-lAP ............................. 47 

Figure 16: Comparison of the XFM and Xact-IAP measured concentrations with the QAGspiked flue gas concentrations during Phase lltesting ........................................................... 49 

Figure 17: Phase ll XFM linearity .......................................................................................... 51 

Figure 18: Phase U Xact linearity ........................................................................................... 54 

figure 19. Comparison ofHg concentrutions determined by XFM and Ontario Hydro 

reference method at a coal-fired power plant ......................................................................... 60 

f igure 20 Plot ofXact-IAP concentration versus Reference Method 29 measured 

concentrations showing excellent agreement over two orders of magnitude and at 

concentrations in excess of 2,000 jig/dscm ............................................................................ 62 

Figure 21. Plot ofPb concentrations determined by Reference Method 29 and the Xact ...... 63 

Figure 22: Comparison of results from laboratory XRF analysis io July, 2002 with Xact field 

test results from May 2002 relative accumcy tests at a hazardous waste incinerator ............. 63 

Medtoc1301 Eval: VI .O Page ix of xii 

VES009479 
List of Tables 

Table 1: Overview of Phase I validation test schedule ........................................................... 10 

Table 2: Acceptance criteria for QAG .................................................................................... II 

Table 3: Overview of Phase II validation test schedule .......................................................... 12 

Table 4: Acceptance criteria for Phase TT validation nfthe XFM and Xact-JAP ................... 12 

Table 5: Comparison of surrogate and Phase II Oue gas characteristics ................................ 14 

Table 6: QAG Emjssion Rates for Phase 1 and ll ................................................................... 36 

Table 7: Flowmeter evaluation during Phase !. ...................................................................... 38 

Table 8: Flowmeter evaluation during Phase 11 ...................................................................... 38 

Table 9: Upscale and zero drift during Phase I cesting ........................................................... 39 

Table 10: Evaluation ofNIST thin-film standards by the Xact-IAP ...................................... 39 

Table II: Upscale and zero drift during Phase II testing ........................................................ 40 

Table 12: Comparison of Average QAG reference aerosol concentrations with XFM and 

X act-lAP average measured concentrations (f.lg/dscm) .......................................................... 42 

Table 13: Lead and chromjum measured on the upstreamPTFE filler as percent of total XFM 

lead and chromjum (IJg/fdter) ................................................................................................. 43 

Table 14: QAG efficiencies determined during Phase I laboratory tests(%) ......................... 45 

Table 15: Summary ofQAG Phase I precision(%) ............................................................... 45 

Table 16 Summary of Phase I QAG validation results ........................................................... 47 

Table 17: Summnry ofXFM and Xact-IAP measun:d concentrations and QAG-spiked flue 

gas concentrations Phase li (IJg/dsem) ................................................................................... 49 

Table 18: Summary ofXFM Phase II bias values for each metal tested (llg/dscm) . ............. 50 

Table 19: Summary of Phase TI XFM validation test criteria and results ............................... 51 

Table 20: Comparison of Xact-IAP with QAO reference concentrations and bias (IJg/dscm) . 

................................................................................................................................................. 53 

Table 21: Summary of Phase TI Xact results .......................................................................... 54 

Table 22: Comparison ofXact Phase n results witb proposed PS-10 criteria ........................ 55 

Table 23. List of stack conditions for which Xact-IAP and XFM tests have been conducted 58 

Table 24. List ofte.•;t condilions and references used to evaluate method applicability ......... 61 

Table 25: Recenl tests ofXact and XFM on wet and dry stacks ............................................ 64 

Table 26: Xact detection limits determined at Lilly's Tl49 incinerator ................................. 66 

Mctbod 30 I E vat. V 1.0 Page xofxii 

VES009480 
J.lg/m' 

As 

Cd 

CEMS 

CES 

CFPP 

CFR 

Cr 

DAS 

DQO 

DSCM 

DSLP 

EPA 

Hg 

HWC 

IAAP 

lAP 

LVM 

M29 

M30 1 

MACT 

MFC 

MFM 

MM-CEM 

MRl 

Pb 

PSlO 

QA 

QAG 

QC 

RA 

List of Abbreviations 

Micro-grams per cubic meter 

Arsenic 

Cadmium 

Continuous Emissions Monitoring System 

Cooper Envirotm1ental Services LLC of Ponland, OR 

Coal Fired Power Plant. 

Code of Federal Regulations. 

Chromium 

Data Acqui;ition System 

Data Quality Objectives 

Dry Standard Cubic Meters 

Dry Standard Liters Per Minute 

United States Environmental Protection Agency 

Mercury 

Hazardous Waste Combustor 

Iowa Anny Anmmnition Plant 

Instrumental analyzer procedure 

Low Volatile Metals (arsenic, beryllium, chromium) 

EPA Reference Method 29 

EPA Reference Method 30 I 

Maximum Achievable Control Technology 

Mass Flow Controller 

Mass Flow Meter 

Multi-metal Continuous Emission Monitor 

Midwest Research Institute, Kansas City, MO 

Lead 

EPA's proposed Performance Standard I 0 for multi-metal CEMS 

Quality Assumnce 

Quantitative Aerosol Generator 

Quality Control 

Relative Accuracy 

Method 301 6\':ll.: VI.O Page xi of xii 

VES009481 
RSD 

slpm 

SVM 

TBAD 

USACERL 

VM 

XCEM 

XFM 

XRF 

Zn 

Relative Standard Deviation (% RSD equals precision) 

Standard Liters Per Minute 

Semi-volatile metals (cadmium, lead) 

Tooele Army Depot 

U.S. Army Construction Engineering Research Library 

Volatile Metals (mercury) 

X-ray based Continuous Emission Monitor 

X-ray based Filter Method 

X-Ray Fluorescence 

Zinc 

"lhOO 30 I E wL: VI .0 Page xii ofxii 

VES009482 
1.0 Introduction 

What is this report abow? 

This report describes a new multi-metals measurement and validation system. It also 

presents the results of tests demonstrating that each of the system components meet the U.S. 

Environmental Protection Agency (EPA) Method 301 criteria for conditional method status. 

The objectives of this report are to present and discuss these results in support of EPA's 

evaluation of this system, and obtain EPA acceptance of its components as conditional 

methods. 

Wiry are we concerned abow metal emissions? 

Air toxic metals have been associated with a wide range of environmental and human health 

effects including respiratory disorders, pulmonary disorders, and cancer. Recent findings link 

air toxic metals with in·\~vo and in-vitro inflammatory responsesu . As such, there is 

continuing concern for potential health effects of metal air pollutants including such metals 

as Sb, As, Cd, Co, Cr, Hg, Mn, Ni, Pb, and Se. The EPA is required to control emissions of 

toxic and hazardous air pollutants under the Clean Air Act Amendments of 199010• Under 

Sections 112(k) and 112( c) or the Clean Air Act, the EPA is also required to monitor the 

ambient air concentrations of these species to evaluate the effectiveness of its reduction 

strategies. For these reasons, the EPA has developed an air toxics objective that includes an 

effort to reduce air toxic emissions and implement area specific control strategies to roduce 

air toxic exposures by 201011

• However, our current understanding of metal emissions is 

relatively poor, primarily because our current measurement technology is inadequate. 

Why is the currenr metals mlUI.Sllreme/11 system inadequaTe? 

A metals emissions measurement system needs to be capable of meeting a range of practical 

requirements in addition to meeting such basic requirements as being accurate, precise, 

reliable and verifiable. Top among practical requirements is that the measurements should be 

timely and representative; that is the results need to be available within a time fiame 

adequate for decisions (hours to days) and representative oflong term emissions (months to 

years). However, the currently accepted reference measurement system consists of one 

method capable of only infrequent periodic measurements; i.e. EPA Reference McU1od 29 

(Method 29). 

This method is considered inadequate and inappropriate for current applications primarily 

because it is not a continuous emission monitoring system (CEMS) and therefore may not be 

adequately representative of long tenn average emissions; but also because of its long 

reporting times, which are typically on the order of several weeks or more. For example, to 

be effective as a quality assurance tool for CEMS validation or trial bum applications, a 

reference method must provide results within hours of the time of sampling or at least by the 

next day so as to allow time for adjustments prior to completing these tests. In addition, it is 

felt that for some metals Method 29 suffers from accuracy aod precision limitations'z. u 

Method 29 is also relatively difficult and dangerous to use, creates large quantities of 

Section 1.0 Introduction Page 1 of40 

VES009483 
hazardous waste, recovered samples are difficult to ship in a post-911 environment, and the 

method is costly. In addition, Method 29 is not consistent with current ambient metals 

measurements and as such more likely to have systematic biases relative to these ambient 

measurements. Because of the above noted limitations of Method 29, candidate alternative 

methods are being proposed. 

What is this new metals measurement system? 

The currently proposed metals measurement system consists of two candidate conditional 

measurement methods, a multi-metal CEMS and a quantitative reference aerosol generator. 

The multi-metals CEMS is not addressed in tl1is report. 

What are these candidate conditional methods? 

The two candidate conditional methods are based on collection of representative samples of 

particle and vapor phase metals on a reactive filter followed by metal determination using Xray fluorescence (XRF) analysis. One is a method of collecting periodic samples by drawing 

stack gas through a series of filters contained in a sealed filter cassette. In this X-ray based 

filter method (XFM), particulate phase metals are trapped on a non-reactive filter while vapor 

phase metals including mercury are collected on a chemically reactive filter or solid sorbent. 

Tbe concentration of metals in the resulting filter deposits are non-destructively determined, 

either in the field or laboratory using XRF analysis following analytical procedures similar to 

those listed in EPA's Compendium Method 10-3.3 ("Detennination of Metals in Ambient 

Particulate Matter Using X-Ray Fluorescence (XRF) Spectroscopy in Compendium of 

Methods for the Determination of Inorganic Compounds in Ambient Air, EP A/625/R96/0lOa, June I999.)14

• The stack gas concentration is calculated by dividing the XRFdetermined metal mass by the volume of stack gas that passed through the filters. The other 

measurement method is an instrumental analyzer procedure (lAP) based on the collection of 

a representative sample of particles and gas phase metals on a reactive filter tape followed by 

determination of metals with XRF analysis (Xact-IAP). 

The other component in this system is a Quantitative Aerosol Generator (QAG). The QAG 

generates a NIST-traceable reference aerosol that can be used, in addition to its other 

applications, to challenge and evaluate the accuracy, precision and linearity of the 

measurement methods and is applicable to non-metal species as well as metal species. 

Wiry are the XFM and Xact-IAP candidate methods more appropriale than Method 29? 

These candidate methods are more appropriate than Method 29 primarily because of their 

rapid analysis tum arowtd times, which can be as short as 15 minutes in the case of the XactIAP or two hours in the case of the XFM if a field-portable XRF analyzer is used. Not only 

do these methods meet the required tum around times, but they also provide better precision 

and accuracy than Method 29 as the results reported in this document demonstrate, and their 

results can be independently verified because the analysis is non-destructive. In addition, the 

methods provide lower detection limits, require fewer resources, are safe and easy to use, 

generate no hazardous waste and are based on well-established EPA analysis procedures that 

are consistent with EPA ambient measurement methods. 

MCit.Od WI £ollt: Vl.O Section 1.0 Introduction Page 2 of40 

VES009484 
Wiry are 1hesc methods imporramto 1he EPA a11d o1her stakeholders? 

We currently have a poor understanding of metals emitted from the country's smoke stacks 

because of the absence of metals CEMS, infrequent manual method measuremems. and 

substantial uncertainty in bow well these measurements represent emissions, operating 

conditions and assumptions. The XFM, Xnct-IAP, and QAO caudidate conditional m~thods 

offer the EPA more convenient and reliable tools for measuring and validating metal 

emissions. This should make it easier for plant operators to make more frequent 

measurements, which will provide the EPA and other stakeholders with a higher level of 

understanding of metal emissions. In addition, this technology should make it easier 10 test 

and evaluate new measurement and control technologies by reducing cost barriers and by 

providing more timely results for engioeeriog evaluation and adjustments. Also, more timely 

resultS provided by these candidate methods during such tests as trial bums will reduce the 

need for repeating these test~ due to extensive delays in receiving Method 29 resultS, which 

are typically not available until after the completion of such tests. 

How was the performance of these methods evaluated? 

A two phased approach was used to evaluate and validate the aerosol generator and the filter 

based measurement methods. Phase I was a laboratory study in which the accuracy, 

precision and linearity of the QAG was established and ruggedness test datu developed for 

the XFM and Xact-IAP. Phase II was a field study conducted to validate the measurement 

methods for applications to stack gases. In Pllase II, the validated QAO was used to generate 

a reference aerosol that was spiked into stack gas, which was subsequently measured with the 

XFM and the Xact-IAP. All of the valid data generated during these tests were used in these 

method evaluations, and far more measurements were taken than required by Metbod 30 I. 

That is, no valid results were excluded in our analysis, even though a subsL"Inrial number of 

resultS could have been omitted while still meeting Method 301 requirements. 

Is this system applicable 10 other sottrces and elements? 

This system is applicable to most emissions from stationary sources and all of the hazardous 

elements as well as all of the elements measured in the ambient environment; including Be if 

it is measured with other analytical methods after non-destructive XRF analysis. 

Where ore the results presented in this report? 

This report presents a summary und discussion of the methods used and test resulls. The 

details of the methods and results are presented in the appendices of this report along witb 

field data sheets, NIST-trnceable cenificatious, sample calculations, all unprocessed data, etc. 

2.0 Approach 

2. I Overview 

The primary objectives of these tests were to validate the QAO as a reference aerosol 

generator and obtain EPA conditional method acceptance for the XFM and Xact-IAP. The 

""'""'""'"'"vo• Section 1.0 Introduction Page 3 of40 

VES009485 
objective of this section is to descnl>e the general approach used to generntc the supporting 

data. and discuss how this approach compares to EPA Method 30 I requirementS and the 

approach proposed in CES' test plan (Appendi>t A). 

2. 2 General Approach 

Neither an appropriate reference method nor performance audit materials were available to 

evaluate the candidate conditional methods. As such, a new appro<tch was required to 

demonstrate the precision and accuracy capabilities of the candidate methods. Although 

ti1ere are numerous standard EPA analytical protocols available that are NIST-traceable, the 

real limitation was in the sample collection part of the sampling and ana y~is procedure. A 

key sampling issue in this case was the need to verify sample c~llection efficiencies to a 

precision and accuracy consistent with the potential precision (<5%) and accuracy (<5%) 

believed to be attainable with the candidate methods. 

A two-phased approach was used in this case as schematically illustrated in Figure I. The 

first phase (Phase I) consisted oflaborotory validation ofCES' QAG, while Phase 11 was a 

field evaluation test of the XFM and Xact-lAP using a reference aerosol generated by the 

validated QAG. The frrst step was the development of a QAG capable of emitting a 

reference aerosol, which could then be validated in the laboratory using independent NlSTtraceable aerosol concentration measurements (Phase I). The QAG, thus validated in the 

laboratory, was then used in the field to spike stack gas with a reference aerosol of NISTtraceable concentration to challenge the candidate conditional measurement methods (Phase 

If}. The success of this approach depended on several key factors including: 

• Independence oftbe NIST-traCC'dble aerosol generation process and the NJSTtraceable aerosol measurement methods. 

• High level of precision for both the generator and the analytical method (about 2%). 

• The resulting small bias between the generator and analytical method (<5%). 

• The magnitude of the bias being on the same order of magnitude as the expected 

uncertainty in the bias established through propagation of errors in both the generator 

and anal}1ical measurements. 

Although under these conditions, the "true" concentration of the generated aerosol was 

"unknown", its concentration was known at least to an accuracy comparnblc to the degree of 

propagated error and independent method agreement or magnitude of the bias; i.e., <.5%, 

which is significantly better than the c>tisting metals reference method. 1110 resulting QAG 

could thus be used in tbe field with a high level of confidence that the generated reference 

aerosol concentration was NIST-traccable to an accuracy of 5% or bener. 

The general validation procedure used is illustrated in the schematic flow diagram shown in 

Figure I. As noted above, a key component of this validation procedure was the fact that the 

QAG not only generated an accurate, NlST-traceable aerosol of known composition, but the 

composition of the generated aerosol was stable over periods of several days as documented 

with the Xact-IAP and XFM performance during evaluation teSting. TI1is documented 

Melhod JOI £y&J.; VI .0 Section 2.0 Approach Page 4 of40 

VES009486 
aerosol stability allowed the determination of precision through the collection of replicate 

sequential samples instead of collection of simultaneous samples using dual sampling trains. 

Phase t 

CES Laboratory 

CESAEROSOL /IJr 

GENERATION SYSTEM 

. High Accuracy - )(act _, XFM I • High Precision -·- - • High Long term Stability . Moasured Precision and " . Phase II Stablity Ully Stack Gas 

Figure 1: Schematic Dow diagram Illustrating key aspects of the general validation 

procedure. 

2.3 Method Independence 

Independence of the aerosol generation and measw·ement methods is essential to the 

approach used to validate the QAG and subsequently the XFM and Xact-lAP. This method 

independence is schematically illust.rntcd in Figure 2. As illlh""tratcd in this figure, the QAG 

generated aerosol concentration is traceable to NIST (Appendix C). In this eliSe, all 

parameters used in the calculation of the aerosol concentration are NTST -rraccable including 

the concentration of the standard solution and the rate of solution use. 

Method JOL Eval.: VJ.O Section 2.0 Approach Puge 5 of40 

VES009487 
NIST 

QAG 

Figure 2: Schematic representation of key components of CES' referrnce aerosol 

generation system. 

The aerosol generation process was evaluated with independent filter samples of the aerosol 

collected by the XFM and Xact-lAP, wlticb were subsequently analyzed by XRF using two 

separate X-ray spectrometers. (Appendices B and D) The XFM and Xact-IAP parameters 

used to determine the volume of aerosol sampled are NIST traceable. (Appendix 0) In 

addition, the XRF parameters used to detennine the mass of metal in the. filler deposit are 

traceable to NIST (NIST SRM 1832 and 1833, and gravimetrically NIST traceable tllin film 

standards) and are independent of the aerosol generation process. These generation and 

measurement methods are clearly independent. Although further traceability or confinniug 

measurements should not be required, additional measurements and routes to traceability 

were established through independent laboratory inductively coupled plasma analysis (ICP) 

of solution and filter samples as illustrnted in the lower ponion of the schema!ic illustration 

shown in Figure 2. The resulting independent laboratory-determined elemental 

concentrations and elemental ratios confumed the standard solution concentrations used in 

~!«bod 301 Em: VJ.O Section 2.0 Approach Page 6 of40 

VES009488 
the QAG. In addition, selected XFM Iiller samples were analyzed by ICP using on 

independent laboratory to confl!IJl the metal deposit measurements made by the XRF 

analyzer. These independent, third party measurements were also used to confum the 

elemental concentrations, their ratios and their N!ST traceability (See Appendix G). It 

should also be noted that the XRF unulyzer used to analyze the XFM filter samples was also 

used in an earlier EPA PM,., speciation program in which numerous "round robin" type of 

quality assurance tests were conducted and demonstrated comparable results to two other 

independent laboratories15. Thus, not only are the aerosol generation and measurement 

methods clearly independent, but tbere is a reasonable degree of independent quality 

assurance between the XFM and Xact meusurement methods. In addition, since two 

different Xacts were used in Phase I and Phase IT testing (CES and Lilly Xacts) requiring rwo 

different calibrations, there is a reasonable degree of independence of these two sets ofXact 

measurements. As a result, when there is a high degree of agreement between the generated 

aerosol concentration and the measured concentration, accuracy of both the genemtor and 

measurement methods are simultaneously validated within the degree of agreement because 

of the independence of their NIST traceability. 

The test procedures used for this validation report were more rigorous and demanding than 

the procedures described in EPA Method 30 l. For example, the Method 30 1-bnsed 

evaluation procedures used here include additional linearity requirements as well as the 

Method 30 I precision and bias requirements. In addition, substantially more measurements 

were made than were required and none of the valid data was excluded from the data 

analysis. Also, because of the mulli-clemental nature of the measurements, inter-elemental 

ratio requirements were added to acceptability criteria. 

2.4 QAG Va/idatwn (Phast! I) 

The experimental arrangement used to validate the QAG during Phase !testing is illustrated 

in the flow diagrams in Figure 3 und Figure 4 (Details of the test and QAG are discussed in 

Appendices A and C). The QAG comr'nents are illustrated on the right side of Figure 4. It 

consists of a Collison-type nebulizer

1 maintained at o•F to minimize water vapor loss from 

tbe NIST -traceable spike solution duriog nebulization and vapor-droplet equilibration. The 

spiking solution was circulated through a large solution reservoir to minimize the impact on 

solution concentration due to loss of water from evaporation. The rate of QAG metal 

emissions was determined by measuring the solution use rate in grams per minute us 

detennined by a NIST -traceable balance and correcting for vapor loss. The resulting 

nebulizer-produced aerosol (about J 5 lpm) passed into a settling chamber where liquid 

droplets greater than about 20 ).lm in diameter settled out of the gas flow and were returned to 

tl1e solution reservoir. The resulting size-selected aerosol was then injected into a drying 

chamber maintained at about 300 °F where it was dried and diluted wit.h about 30 to 50 lpm 

of clean, dry laboratory air. The dry salt and metal vapor containing aerosol emerging from 

the QAG was diluted further with about 20 to 40 lpm of make-up air. The reference aerosol 

total flow was about 100 to 120 lpm, o.nd was monitored with a NlST-traceable mass flow 

meter. 

Mclhod301 Evst: VJ.O Section 2.0 Approach Page 7 of40 

VES009489 
MAKE-UP 

AIR rl 

'--"" . r---·· I 

QUANTITATIVE 

AEROSOL 

GENERA TOK (QAG) 

QAG _ j 

AIR 

SOLUTION 

RESERVOIR 

TO 

EXHAUST f TOTAl. F.LOW 

EXHAUST 

_l')ANIFOLD ! 

Xact AP 

XACf STILLING 

CHAMBER 

t 

I BYPASS I I 

l -- O~_j ! 

h_ ;;: \ i i ---,....---_: ·· ··~ ~:;~~; H.J XFM 1-' L ____ __ 

XACTMETALS 

ANALYZER 

QAG V AL!DATION 

• Percent Transport 

• Pb and Cr Filter Ratios 

• Elementa I Ratios 

BALANCE ~ SOLUTION I; 

L-------~· L_ USERATE _ _ _ _.J 

• Precision 

• Linearity 

Figure 3: Flow diagram showing the experimenta l arr angemen t used to validate the 

QAG reference aerosol gener ator. 

The QAG-generated reference aerosol contained five metals, (As, C.d, Cr, Pb, and Hg) 

representing the volatile, semi-volatile and low volatility metal categories as defined in the 

Hazardous Waste Combustor (HWC) Maximum Achievable Control Technology (MACT) 

rule17• Aerosol concentilltions ranged from 20 to more than 120 l'g/dscm, spanning the range 

of their MACT emission limits. This reference aerosol was directed from the QAG to the top 

of the Xact stilling chamber through 2-incb diameter stainiess steel (SS) tubing. About 99"/o 

of the flow passed through the test apparatus and was filtered prior to flow measurement. 

Less than l% of the reterence aerosol w·as sampled from the stiUing chamber by the XactIAP (about 0. 7 slpm). During XFM testing, almost 40% of the sample flow was dillwn 

through the XFM plenum and returned to the exl1aust downstream of the stilling chamber. 

From this subflow, about I lpm of the reference aerosol was sample.d and drawn through the 

MC1hod 301 E"al.: VJ.O Section 2.0 Approach Page 8 of40 

VES009490 
Exhaust Aetoeol 

fifiM 

1 • 

liiiQ'I; • ' 

D ·I[] 

i • t -· --- ![I 

• • 

Figure 4: Schematic representation of the e¥J>erimental arrangement used in Phase I to 

validate the QAG reference aerosol generator. 

XFM filter cassette. The resuhing XFM fLiters were analyzed by XRF using EPA 

Compendium Method 10-3.3 for panicle deposits on filters while the CES Xact-IAP 

automatically reported metal concentmtions every 15 minutes for the dun~rion of the test. 

Typical test periods consisted of establishing a stable reference aerosol flow through the 

Xact-JAP Stilling chamber and out the exhaust manifold. The concentration of this reference 

aerosol was stable to within a few percent during each series of test runs as demonstrated by 

the Xact and QAG combined precision, which was typically on the order of2 to 4 %. The 

aerosol metal concentrdtion in the stilling chamber was simultaneously sampled and 

measured by both the Xact and XFM, wbicb provided independent confirmation of the QAG 

reference aerosol concentrations. During I inearity evaluation tests, the aerosol concentmtion 

was increased or decreased by changing the spiking solution concentration. 

Phase I validation testing of the QAG was conducted at CES' laboratory using spiked 

ambient air. During these tests, the QAG spiked five MACT metals (As. Cd, Cr, Pb and Hg) 

at five concentration levels, including a series of blank runs, which were then compo.red to 

the measured concentrations reported by the CES Xact-IAP and the XFM. During Phase I, a 

total of26 XFM and 148 Xact runs were compared to the QAG reference concentrations 

(Table 1). 

MethodJOl E-.~1.: VI.O Section 2.0 Approach Page 9 of40 

VES009491 
Table 1: Summary of QAG validation test schedule. 

Nominal Nominal No. of 

Date 

Level for QAG Conc. XFM No ofXact 

MACf Runs 

Runs 

Metal )Jgldscm 

Dec. 14-15,2004 Mid2 65 12 93 

Dec. 16, 2004 Midi 50 4 13 

Dec. 16, 2004 Low 20 4 12 

Dec. 16, 2004 High 130 4 lJ 

Dec. 17, 2004 Blank 0 2 19 

Total Ru ns 26 148 

The validation metrics or criteria used to establish the validity of the QAG are listed below: 

• Transport Efficiency: The calculated transport efficiency shall be greater than 80% 

for all elements. Since the NIST -traceable reference aerosol concentration is totally 

independent from the NIST-traceable filter sampling and analysis method, this 

criterion, if met, might be considered adequate to establish an acceptable efficiency 

correction factor for the QAG. 

• Lead and Cr Filter Ratios: To ensure that the filters had adequate particulate 

trapping efficiency, less than two percent ofd1e Pb and Cr were permitted on the 

XFM reactive filter downstream of the PTFE filter. This plus the assumed low 

volatility of these elements will assure a near 100% sample train trapping efficiency 

for these elements. This criterion plus the following criterion provide additional 

assurance that the trapping efficiencies for all of the elements are near I 00%. 

• Elemental Ratios: As, Cd, Cr, and Hg concentration ratios to lead measured in the 

aerosol sample must be within ±I 0% of the concentration ratios in the QAG solution. 

Meeting this criterion assures not only high trapping efficiencies but also high 

generation and transport efficiencies for aU of the elements including volatile 

elements. 

• Precision: The QAG must have a precision, as measured by percent relative standard 

deviation (PRSD), of less than I 0% for each of the elements. This high precision 

criterion will enable sequential sampling of the candidate methods at each 

concentration level. 

• Linearity: The QAG and both candidate tllter-based conditional methods shall have 

a correlation coefficient (r) that is greater than 0.85. This criterion shows that the 

QAG is linear over a wide range of concentrations. 

These criteria and their acceptable ranges are summarized in Table 2. 

Method 301 E\·:.1.: V 1.0 Section 2.0 Approach Page 10 of 40 

VES009492 
Table 2: Acceptance criteria for QAG. 

Criteria Measure No. Runs Acceptable Ra nge 

Filter Ratio back to front ratio (Cr, PB) >9 <0.02 

Metal Ra tio solution to aero::>ol ratio >9 0.9to I. I 

Efficie.ncy t·statistic >9 < critical value or 

efficiency faclor >9 'Between 0.8 and 1.0 

Precbi on percent of spiked cone. >9 <10% 

Linearity cflrrclation coefficient >9 >0.85 

These criteria include required bias (efficiency) and precision validation paramelers from 

Method 30 I (bias or in this case efficiency and precision) and additional validation indicators 

relevant to these specific tests: i.e., filter ratio, metal ratio and linearity criteria. The 

acceptability ranges listed in Table 2 were guided by values required by Method 30 I, 

Perfonnance Specifications I I and proposed Performance Specification 10, and are either 

equal to those listed in these procedures or are more restrictive. 

2.5 XFM and Xact-IAP Validation (Phase ll) 

The primary objective of Phase II testing was to validate the XFM and Xact-TAP while 

sampling flue gas. Tite validity of these sampling and analysis methods was evaluated by 

comparing the Phase I validated QAG reference aerosol concentration with the XFM and 

Xact-IAP measured concentrations. It is important to note that a different Xact instnunent 

was used in Phase 11 than was used in Phase I. 

Following Phase I testing, the QAG was installed at a hazardous waste incinerator18 and a 

series of validation tests were conducted. During these tests, the QAG reference aerosol was 

spiked into incinerator flue gas at four different concentration levels while an XFM sampling 

train and Xact-IAP were collecting simultaneous samples from the Xact stilling chamber. 

Tbe experintental arrangement was similar to that used in the laboratory with the primary 

difference that the reference aerosol was spiked into stack gas instead of laboratory air. In 

addition, the Xact used in these field tests was different from the one used during the Phase I 

tests at CES' laboratory. During Phase U, the QAG spiked five MACT metals at four 

concentration levels (Table 3) into about 35 slpm of flue gas while the XFM and Xact-IAP 

concurrently sampled the reference aerosol spiked stack gas. A total of 24 XFM and 192 

Xact-IAP runs were completed during Phase n tests while the QAG was operating. 

Section 2.0 Approach Page II of40 

VES009493 
Table 3· Overview of Phase ll validation test schedule . Nominal Nomin:d QAG No.of XFM No ofXact 

Date· Level Cone. Runs Runs 

lll!fdscm 

March 4· 5, 2005 High lOR 12 45 

March 6, 2005 Low 21 4 46 

March 7, 2005 Mid 45 4 37 

M:rrch 8, 2005 Blank 0 4 64 

Total Ruos 24 192 

Validation criteria used to evaluate the acceptance of the XFM and Xact-IAP were similar to 

those used for the QAG in Phase I and are listed in Table 4. These criteria include bias, 

precision and linearity of the measurement methods. The main difference was the omission 

of the filter and elemental ratio criteria, which were not relevant to Phase U testing. As was 

the case in Phase I, the acceptability ranges listed in Table 4 were guided by values required 

by Method 301, Performance Specifications 111

s and proposed Perfonnance Specification 

1 <flO, and are either equal to those listed in these procedures or are more restrictive. 

Table 4: Acceptance criteria for Phase II validation of the XFM and Xact-IAP. 

Criteria Measure No. Acceptable Range 

Measurements 

Bias 

!-statistic >9 < critical value or 

correction factor >9 Between 0.8 and 1.2 

Precision percent of emission limit >9 <10% 

Linearity correlation coefficient >9 >0.85 

2.6 Del'iationsfrom Test Plmt 

The original draft Test Plan was developed in the fall of2004 to organize validation testing 

of the XFM and can be found in Appendix A. During actual testing, there were five 

significant deviations from this test plan. Why these deviations occurred and any potential 

impacts to the resulting data set are discussed below. 

• Evaluation of the Xact-IAP: The test plan proposed an approach for validating the 

QAG and XFM, but it did not focus on the Xact-!AP as a separate Instrumental 

Analyzer Procedure. Following discussions with the EPA, the scope of the test was 

expanded to include the Xact-IAP, following the same validation criteria as the XFM. 

Both the XFM and the Xact-IAP are candidate conditional methods, but the Xact-IAP 

offers end-users more immediate feedback. For this reason, and since the same QAG 

data set could be applied to both approaches, the test plan was expanded to include 

validation procedures for the Xact-IAP. 

• Total Capture: The original test plan proposed using a total capture approach to 

validate the QAG in Phase I. The total capture approach, however, was technically 

Method 301 Eval : VI.O Section 2.0 Approach Page 12 of 40 

VES009494 
problematic and was not used during the validation tests. Instead, the approach used 

was based on independent measurements of the resulting QAG generated aerosol 

concentration as described above. 

• Bla11k Runs: The original test plan called for injection of water for blank nms to 

determine XFM detection limits. During the course of testing, it was determined that 

pure water would freeze in the QAG. For this reason, blank 5% nitric acid was spiked 

instead of water. These blank tests were conducted during both Phase I (five hours) 

and 11 (eight hours). This blank testing resulted in six XFM and about 100 Xact blank 

test runs. Although all five metals reported blank concentrations ofless than one 

~dscm for the XFM and the Xact-IAP, acrual detection limits were calculated using 

a much larger data set (Appendix K) and then compared to the blank runs as 

discussed in Section 7 .11.2. 

• Precision: The precisions measured for the QAG, XFM, and Xact-IAP were based on 

the PRSD of the measured metal concentrations when the QAG was spiking at a 

constant rate. The original test plan called for calculation of precision as a percent of 

the emission limit, and tl1e results indicate that calculating precision in this manner 

would have met the test plan precision criteria of 10%. However, since a range of 

concentrations were used to detennine linearity, a more demanding protocol using all 

of the data including the lowest spiked concentrations was used that divided the 

standard deviation at each concentration by the mean concentration at each spiked 

level. This latter approach is consistent with Method 301: Equation 301-622• 

• Flue Gas Composition: Phase 11 samples were collected when the incinerator was 

burning narurnl gas instead of waste. In the week prior to Phase ll testing, cracks were 

observed in a section of incinerator piping that is exposed to pressures of more than 

I 000 PSL These cracks precluded the burning of waste during testing and, since it 

was a two to three month delay before the pipes could be repaired, it was decided to 

conduct the tests using narural gas rather than delay the tests. A comparison of the 

flue gas characteristics for Phase 11 tests relative to flue gas characteristics during 

surrogate feed stock bums conducted in the Fall of2004 is shown in Table 5. In 

general, the incinerator emissions produced while buming narural gas in Phase II 

were very similar to those observed during the surrogate feed stock burns. Most major 

flue gas species such as S02, H20, CO, and C()z, were found in the same or higher 

concentrations during Phase 11 tests than in the surrogate feed stock bum tests in the 

fall of2004. The primary difference was a decrease of 64% in particulate 

concentrations during Phase II tests. However, the impact of this parameter is 

insignificant at these concentrations (less than I Omgldcsm @ 7% 0 2), and would not 

be significant unless it were well over the permitted PM emission limits. 

Section 2.0 Approach Page I3 of 40 

VES009495 
T a bl e 5 : C ompan son o f surro2ate an d Ph ase II f1 ue I!&S character lstl cs. 

Cbetuical SuOTogate. TesiS Phase II PhaseD 

Sp<cies Fall 2004 March 2005 Surrogote Rodo 

sob dry· (ppm) NO ± NO ND ± NO -~~~----

HCI, dry (ppm) 2.3 ± 1.2 1.9 ,. 06 0.8 

CO,, dry· (%) 8.3 ± 0.7 6.0 :i: 0.1 0.7 

CO, dry (ppm) 8.4 :1: 1.9 13.8 ± 0.7 1.7 

o ,, dry(%J 9.1 ± 0.9 11.4 ± 0.1 13 

H,O (%) 9.2 ± 3.3 10.1 ± 0.4 1.1 

PM @7% 0 , 9.8 ± 2.8 3.5 ± 0.4 0.4 (mgtdsem) 

NO., dr)' (ppm) 40.5 ± 10.0 108.1 :i: s.s 2.7 

Flow (dscfm) 14196 ± 1096 9952 ± 423 0.7 

3.0 Methods 

3.1 QAG Rejere11ce Aerosol Generator 

The reference aerosol used in these tests was generated with CES' quantitative aerosol 

generator (QAG). This aerosol was the primary reference source used to determine bias and 

precision capabilities of the candidate conditional multi-metals methods. The QAG provides 

a continuous reference aerosol whose analyte concentration is NIST -traceable widt 

documented accuracy and precision. Ouce validated iu the laboratory during Phase I testing, 

the QAG was used to spike incinerator slack gas in the field during Phase ll testing. 

Although the QAG has the ability to generate a wide range of analyte-containing aerosols, 

tbe only type used in the experiments described in this report were metal containing aerosols. 

The QAG generates its reference aerosol using the following three basic steps: 

• First, an aerosol of anal)1e solution droplets is created using a nebulizer16

. 

• This is followed by the separation and recirculation of large droplets using a settling 

chamber where the large droplets are removed while liquid and vapor phases are 

equilibrated. 

• The third step consists of drying droplets smaller than 20~tm in diameter. 

Method JOJ £\•3.1.: VI.O Section 3.0 Methods Page 14 of40 

VES009496 
The dried analyte-containing aerosol emission rate is calculated from the analyte 

concentration in the nebulized solution, the solution droplet emission rate, and the total 

volume of nebulizing, drying and dilution gas used to create the resulting aerosol. Use of 

nebulizers to generate quantitative aerosols is typically limited by three key factors: 

• The magnitude and uncertainty of the water vapor emission rate lost during droplet 

generation and equilibration 

• Changing solution concentration due to evaporation of solution 

• Generation oflarge droplets, which can represent a significant fraction of the emitted 

mass and could have low transport efficiency due to the large size of the resulting 

dried salt particles. 

These potential problems have been effectively either eliminated or minimized in the current 

model of the QAG by (I) generating the droplet aerosol at 32° Fusing cooled water-saturated 

nebulizing air to minimize and quantify the evaporative component, (2) using a large solution 

reservoir to both minimize the impact of changing concentration due to evapOrdtiOn and to 

allow for measurement of total solution use rate, and 3) incorporation of a stilling chamber to 

separate and recycle large solution droplets. 

Key QAG components are illustrated wid1 the schematic drawings shown in Figure 5. 

Quanlilll.liv.: 

AtrCSbl 

i. ::.. 

DJyina 

<lamb" 

i. ::.. 

Soollngl 

&:;uililx'ati.ng 

"""'"'" 

i. I 

C(IIIISI"" 

l)'pt 

Ncblllita 

·j · /' 

~ 

~ 

Pucnp ~ 

i. I lJ I 

! COIIIY~oo 

Nt'buti:u:r 

S!.nn(hlrd ---1' T(I'J'II'¢iWre A Nebl!llza Ait Solutjon ('c.mtmUcd 

Coolrol --,... }(e b."lth " Control 

SoJutXl.u 

Rf.Se __ fVolr , -· Itt ibth 

B~'!_nC(< 

A. B. 

Ca""d 

Elubbl.<'f" 

Eltt\'fllll 

8 ubbler 

g 

Figure 5: A. Schematic of flow through QAG components. B. Overview of the set-up of 

QAG components. 

MNl!od30l EvoL: Vl.O Section 3.0 Methods Page 15 of40 

VES009497 
There are six major components of the QAG: 

• A reference solution control component is used to circulate the analyte-containing 

solution through the nebulizer and measure the total solution use rate. This 

component consists of a peristaltic pwnp, solution reservoir, balance, connecting 

tubing and a laptop used to record the balance re-ading every 15 seconds. 

• A nebulizer air control component used to maintain and measure the flow, 

temperature, pressure and saturation of air used in the nebulization process. This 

component uses compressed air at about 20 PSI-gage pressure to force air through the 

nebulizer. The nebulizing air passes through flow and pressure regulators, an external 

bubbler to saturate the air at room temperature and then a second bubbler to assure 

that the nebulizing air is saturated a 32° F prior to entering the nebulizer. 

• A temperature control component (ice bath) is used to control the temperature of the 

nebulizer air, the nebulizer and the settling/equilibrating chamber at 32° F. 

• A Collison-type nebulizer16 component is used to create the solution droplet aerosol. 

It consists oftbree major components: the nebulizer cup, the nebulizer and nebulizer 

nozzle as describe in more detail in Appendix C. The nebulizer cup contains the 

standard solution. This solution is continuously circulated from the nebulizer cup to 

an external reservoir to minimize the impact of vapor loss on solution concentration 

and to allow for determination of the solution use rate. 

• A settling/equilibrating chamber component located just above the nebulizer 

component. Tite nebulizer-generated aerosol is directed into this chamber where 

large droplets settle from the gas stream and the remaining droplets equilibrate with 

water vapor prior to entering dte drying chamber. The nebulization process creates a 

droplet spray containing a wide range of droplet sizes. The largest droplets impact on 

the walls of the nebulizer cup and are recycled. The smaller droplets are entrained in 

the nebulizer air flow and pass into the settling-equilibration chamber. The function 

of the settling-equilibration chamber is to remove and recycle all droplets greater than 

about 20 11m in diameter as well as to assure droplet-vapor equilibrium at 32°F. 

Thus, the only droplets emitted into dte drying chamber have diameters less dtan 20 

11m and have been equilibrated \\~th water vapor at 32°F. 

• A drying chamber component with temperature and flow controls. In this chamber, 

the size-restricted and vapor equilibrated aerosol from the settling/equilibrating 

chamber is surrounded by dry air at about 300° F, which is used to dry the reference 

solution droplets prior to being emitted from the QAG. The aerosol exiting the 

drying chamber consists of the transport gas (air), water and metal vapor and dried 

salt particles. The size of the salt particles is controlled by the analyte solution 

concentration, the design of tlte settling chamber and the flow rate of nebulizer air. 

This aerosol is the reference aerosol produced by the QAG. However, in this 

experiment, the aerosol was further diluted with makeup air prior to being transported 

to the Xact stilling chamber from which both Xact-IAP and XFM samples were 

drawn. QAG efficiencies referred to in this report are combination generation 

Me:chod 301 Ev<tL: VI,() Section 3.0 Methods Page 16 of40 

VES009498 
(aerosol emitted from the drying chamber ofdte QAG) and transport to the Xact 

stilling chamber. 

The QAG's generated aerosol concentration ( q<J.<G) is process traceable to NIST through 

the traceability of its components (see Appendix C). As demonstrated in Equation 1 below, 

the generated concentration is a function of the solution standard concentration of the 

( c;-0·'c ), total flow rate (F,), rate of mass loss of the solution (R.,), and rate of vapor Joss 

(R,). Process traceability to NTST is established by using instruments that are NIST -traceable 

(e.g., calibrated with NIST standards) to measure these parameters and a solution with NTSTtraceable concentrations. 

The fmal product of the QAG is an aerosol containing dried salt particles and vapors of the 

analyte or analytes. The concemration of the analytes in the aerosol and the concentration 

uncertainty are calculated from the QAG's recorded operating parameters. The equation for 

calculating the generated aerosol concentration is as follows: 

c s-QAG 

c~-{)AG = , (R _ R J 1 F m v 

I 

Equation 1 

Where: 

C~-'G = Concentration of the i"' element in the reference ' aerosol generated by the QAG 

c;..e-'c = Concentration of the i

111 element in lhe QAG's NIST-traceable 

solution 

F, = Total combined tlow of the nebulizer air, drying air and malceup 

air or stack gas 

/1.., Total rate of solution mass loss for the QAG, determined from the 

slope of a linear least squares fit of the reservoir mass data over the 

period of a test or series of tests 

R,. = Rate of vapor loss from the reference solution, as calculated using 

the following equation: 

Equation 2 

Where: 

F, Plow of expanded nebulizer air in the QAG 

M, = Mass of water vapor io a liter of saturated air at 32°F 

Melh<>d 301 Eval.: V 1.0 Section 3.0 Methods Page 17of 40 

VES009499